CN106459276B - Heterophasic propylene copolymers with low extractable - Google Patents
Heterophasic propylene copolymers with low extractable Download PDFInfo
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- CN106459276B CN106459276B CN201580016127.5A CN201580016127A CN106459276B CN 106459276 B CN106459276 B CN 106459276B CN 201580016127 A CN201580016127 A CN 201580016127A CN 106459276 B CN106459276 B CN 106459276B
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- China
- Prior art keywords
- raheco
- propylene copolymers
- heterophasic propylene
- alpha
- propylene
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 229920001577 copolymer Polymers 0.000 title claims abstract description 216
- 239000004711 α-olefin Substances 0.000 claims abstract description 203
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 121
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 55
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 127
- -1 polypropylene Polymers 0.000 claims description 84
- 239000004743 Polypropylene Substances 0.000 claims description 80
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 65
- 239000005977 Ethylene Substances 0.000 claims description 65
- 239000000126 substance Substances 0.000 claims description 64
- 229920001155 polypropylene Polymers 0.000 claims description 56
- 239000000178 monomer Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 31
- 230000009477 glass transition Effects 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 239000003426 co-catalyst Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
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- 150000001450 anions Chemical class 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
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- 239000013110 organic ligand Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 241001274660 Modulus Species 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229920001384 propylene homopolymer Polymers 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
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- 229920000642 polymer Polymers 0.000 description 41
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 33
- 125000000217 alkyl group Chemical group 0.000 description 26
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- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 13
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 6
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 5
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- 239000004698 Polyethylene Substances 0.000 description 4
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- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 4
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- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical group O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 3
- QEOSCXACXNFJCY-AKHDSKFASA-N (2R,3R,4S,5R)-6-benzyl-7-phenylheptane-1,2,3,4,5,6-hexol Chemical compound C(C1=CC=CC=C1)C(O)([C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)CC1=CC=CC=C1 QEOSCXACXNFJCY-AKHDSKFASA-N 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- SGVUHPSBDNVHKL-UHFFFAOYSA-N 1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/17—Viscosity
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Abstract
One kind includes propylene C4~C12Heterophasic propylene copolymers of the alpha olefin copolymer as matrix, wherein, ethylene propylene rubber is scattered in the matrix, and the heterophasic propylene copolymers have good mechanical performance and low extractable.
Description
Technical field
The present invention relates to a kind of novel heterophasic propylene copolymers (RAHECO), its preparation and by its product obtained.
Background technology
In packaging field, polypropylene plays an important role.Commonly using so-called heterophasic polypropylene, i.e. rubber disperse
In semi-crystalline polypropylene matrix therein.This material offers good rigidity and shock resistances；However optical property may be non-
It is often relied on the accurate adjusting of the dispersibility of the rubber in matrix.Further, amorphous fraction can generate a large amount of extractable.
However, the packaging material in packaging material, particularly food industry or the packaging material for medicine/health product, need
With low extractable.On the other hand, as mentioned, packaging material must be that mechanics is stablized certainly.This material
Another critical aspects are its optical properties, i.e., must have acceptable haze value.Performance needed for some is with the side of contradiction
Formula is presented, that is, improves the implementation that a kind of performance will reduce another performance.
Invention content
Therefore, the purpose of the present invention is to provide a kind of polypropylene with low extractable, are that mechanics is stablized, and
And with good optical property.
Present invention finds a kind of heterophasic propylene copolymers, have：Propylene-C as matrix4~C12Alpha-olefin copolymer
Object and the elastomeric propylene ethylene's copolymer being dispersed in the matrix.Preferably, elastomeric propylene ethylene's copolymer has
The ethylene of suitable high-content.
Therefore, the present invention relates to a kind of heterophasic propylene copolymers (RAHECO), it includes：
(i) matrix (M) is propylene-C4~C12Alpha olefin copolymer (C-PP), the propylene-C4~C12Alpha-olefin is total to
Polymers (C-PP) includes the unit from following substance：
(i.1) propylene and
(i.2) at least one C4~C12Alpha-olefin；And
(ii) elastomeric propylene copolymers (EC) being scattered in the matrix (M), elastomeric propylene copolymers (EC) packet
Containing the unit from following substance：
(ii.1) propylene and
(ii.2) ethylene and optional at least one C4~C12Alpha-olefin；
The heterophasic propylene copolymers (RAHECO) have：
(a) the melt flow rate (MFR) MFR measured according to ISO 11332(230 DEG C) are in the range of 2.5~200.0g/10min
It is interior；
(b) total comonomer content is in the range of 12.0~35.0wt%；
(c) according to the amount of the cold soluble matter of dimethylbenzene (XCS) fraction of (25 DEG C) of ISO 16152 measure for 10.0~
40.0wt%；
Wherein, further, propylene copolymer (RAHECO) meets：
(d) inequality (I)
Wherein,
C2 (total) is the ethylene contents [wt%] of heterophasic propylene copolymers (RAHECO)；
Cx (total) is the C of heterophasic propylene copolymers (RAHECO)4~C12Alpha-olefin content [wt%].
It is apparent by the language of aforementioned paragraphs：Propylene-C4~C12Alpha olefin copolymer (C-PP) and elastomeric propylene copolymerization
Object (EC) is different in chemistry.It is therefore preferred that propylene-C4~C12Alpha olefin copolymer (C-PP) does not include from ethylene simultaneously
Unit.It is highly preferred that propylene-C4~C12Alpha olefin copolymer (C-PP) only contains a kind of C4~C12Alpha-olefin.On the other hand,
Preferably, elastomeric propylene copolymers (EC) are ethylene-propylene rubber (EPR).
Preferably, the ethylene contents [wt%] of total heterophasic propylene copolymers (RAHECO) are in the model of 12.0~33.0wt%
Enclose the C of interior and/or total heterophasic propylene copolymers (RAHECO)4~C12Alpha-olefin content [wt%] is 0.5~6.0wt%'s
In the range of.
Particularly, heterophasic propylene copolymers of the invention are characterized in that：The performance of the cold soluble matter of dimethylbenzene (XCS) fraction
And the cold insoluble matter of dimethylbenzene (XCI) fraction.Therefore, the cold soluble matter of dimethylbenzene (XCS) of heterophasic propylene copolymers (RAHECO)
Fraction has：Based on the weight of the cold soluble matter of dimethylbenzene (XCS) fraction, total comonomer content and/or ethylene contents 30~
In the range of 90wt%；And/or according to the inherent viscosity (IV) that DIN ISO 1628/1 (in naphthalane, at 135 DEG C) are measured for extremely
Few 1.2dl/g.
In one preferred embodiment, the cold insoluble matter of dimethylbenzene (XCI) grade of heterophasic propylene copolymers (RAHECO)
Dividing has：Based on the weight of the cold insoluble matter of dimethylbenzene (XCI) fraction, total comonomer content [wt%] is in 3.0~12.0wt%
In the range of；And/or have：Based on the total weight of the cold insoluble matter of dimethylbenzene (XCI) fraction, ethylene contents [wt%] 2.0~
In the range of 11.0wt%；And/or the total weight based on the cold insoluble matter of dimethylbenzene (XCI) fraction, C4~C12Alpha-olefin content
[wt%] is in the range of 0.5~6.0wt%.
It is more preferred still that the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO) meets inequality
(II)：
Wherein,
C2 (XCI) is the ethylene contents of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
Cx (XCI) is the C of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)4~C12α-alkene
Hydrocarbon content [wt%], preferably 1- alkene content [wt%].
In in terms of one further preferred, heterophasic propylene copolymers (RAHECO) according to the present invention meet：
(a) inequality (III)：
Wherein,
C (XCS) is that the total comonomer of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO) contains
It measures [wt%]；
C (total) is the total comonomer content [wt%] of total heterophasic propylene copolymers (RAHECO)；
And/or
(b) inequality (IV)：
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C2 (total) is the ethylene contents [wt%] of total heterophasic propylene copolymers (RAHECO)；
And/or
(c) inequality (V)：
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C (XCI) is that the total comonomer of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO) contains
It measures [wt%]；
And/or
(d) inequality (VI)：
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C2 (XCI) is the ethylene contents of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)
[wt%].
Preferably, the matrix (M) of heterophasic propylene copolymers of the invention (RAHECO) includes two different polymer groups
Point.It is therefore preferred that propylene-C4~C12Alpha olefin copolymer (C-PP) is made of comprising following substances, preferably following substances：
First polypropylene component (PP1) and the second propylene-C4~C12Alpha olefin copolymer component (C-PP2), preferably wherein, further
Ground, the first polypropylene component (PP1) and the second propylene-C4~C12Weight fraction between alpha olefin copolymer component (C-PP2)
[(PP1)/(C-PP2)] is in the range of 30/70~70/30.
Preferably, propylene-C4~C12Co-monomer content, preferably C in alpha olefin copolymer (C-PP)4~C12Alpha-olefin
Content [wt%] is higher than in the first polypropylene component (PP1)；And/or first polypropylene component (PP1) and propylene-C4~C12α-
Co-monomer content, preferably C between olefin copolymer (C-PP)4~C12Alpha-olefin content differs at least 1.5wt%；And/or
First polypropylene component (PP1) and the second propylene-C4~C12Comonomer between alpha olefin copolymer component (C-PP2) contains
Amount, preferably C4~C12The content difference at least 2.5wt% of alpha-olefin.
It is more preferred still that the first polypropylene component (PP1) be propylene homopolymer component (H-PP1) or it is particularly preferred that
First polypropylene component (PP1) is the first propylene-C4~C12Alpha olefin copolymer component (C-PP1), it is preferable that described the one the third
Alkene-C4~C12The C of alpha olefin copolymer component (C-PP1)4~C12Alpha-olefin content is in the range of 0.5~4.0wt%.
Then, it is preferable that the second propylene-C4~C12The C of alpha olefin copolymer component (C-PP2)4~C12Alpha-olefin content
In the range of 2.0~15.0wt%.Therefore, in a specific embodiment, propylene-C4~C12Alpha olefin copolymer (C-
PP co-monomer content), preferably C4~C12The content of alpha-olefin is in the range of 1.5~9.0wt%.
Preferably, the co-monomer content of the elastomeric propylene copolymers (EC) of heterophasic propylene copolymers (RAHECO), preferably
Ethylene contents are in the range of 40~90wt%.
In one preferred embodiment, heterophasic propylene copolymers (RAHECO) meet inequality (VII)：
Wherein,
C (XCS) is the total comonomer content [mol%] of heterophasic propylene copolymers (RAHECO)；
XCS is the content [wt%] of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO).
In another embodiment, heterophasic propylene copolymers (RAHECO) according to the present invention have the first glass transition
Temperature Tg (1) and the second glass transition temperature Tg (2), wherein, first glass transition temperature Tg (1) is higher than the second glass
Glass transition temperature Tg (2), it is preferable that between the first glass transition temperature Tg (1) and the second glass transition temperature Tg (2)
Difference be at least 20 DEG C.Preferably, the first glass transition temperature Tg (1) is in the range of -5~+12 DEG C and/or second
Glass transition temperature Tg (2) is in the range of -45~-25 DEG C.
In one aspect of the invention, heterophasic propylene copolymers (RAHECO) are through α-nucleation.
Preferably, heterophasic propylene copolymers (RAHECO) have：
(a) it is at least 500MPa according to the ISO 527-1 stretch moduluses measured,
And/or
(b) 3.0wt% is less than according to the hexane extractable content that FDA methods measure in 100 μm of casting films.
The invention further relates to the products for including heterophasic propylene copolymers as defined herein (RAHECO), it is preferable that institute
It states product and is selected from the group being made of (medicine) bag, food packaging articles, film and bottle.
Finally, invention further describes a kind of method for preparing heterophasic propylene copolymers as described herein (RAHECO),
It includes the following steps：
(I) polypropylene and C4~C12Alpha-olefin (preferably 1- alkene), so as to form matrix (M), (it is propylene-C4~C12
Alpha olefin copolymer (C-PP))；And：
(II) then, preferably in the gas phase, polypropylene and ethylene, optional at least one C4~C12Alpha-olefin, so as to
Formation is scattered in the elastomeric propylene copolymers (EC) in the matrix (M)；
Wherein, step (I) and step (II) both carry out in the presence of identical unit point solid particle catalyst,
The unit point solid particle catalyst is preferably without outer carrier, more preferably in the presence of the catalyst comprising following substance
It carries out：
(i) transistion metal compound of formula (I)
Rn(Cp’)2MX2 (I)
Wherein,
" M " be zirconium (Zr) or hafnium (Hf),
Each " X " independently is univalent anion σ-ligand,
Each " Cp ' " is cyclopentadienyl type organic ligand, independently selected from group constituted by the following substances：
Substituted cyclopentadienyl group, the indenyl of substitution, the tetrahydro indenyl of substitution and substituted or unsubstituted fluorenyl, it is described
Organoligand coordination in transition metal (M),
" R " is the divalent bridging group for connecting the organic ligand (Cp '),
" n " be 1 or 2, preferably 1 and
(ii) co-catalyst, it includes the compounds of the 13rd race's metal, such as Al compounds or boride.
It is highly preferred that step (I) includes：Polypropylene and optional C4~C12Alpha-olefin (preferably 1- alkene), so as to shape
Into the first polypropylene component (PP1), then polypropylene and C in another reactor4~C12Alpha-olefin (preferably 1- alkene), from
And form the second propylene-C4~C12Alpha olefin copolymer component (C-PP2), the first polypropylene component (PP1) and the second propylene-C4
~C12Alpha olefin copolymer component (C-PP2) forms propylene-C4~C12Alpha olefin copolymer n (C-PP).
In the following, first embodiment and second embodiment will be described in more detail together.
Specific embodiment
The present invention relates to a kind of heterophasic propylene copolymers (RAHECO).More accurately, the present invention relates to a kind of heterophasic propylenes
Copolymer (RAHECO), it includes：Matrix (M) i.e. propylene-C4~C12Alpha olefin copolymer (C-PP) and the bullet being dispersed therein
Property propylene copolymer (EC).Therefore, content of the matrix (M) containing (thin) dispersion for being not matrix (M) part, and
The content contains elastomeric propylene copolymers (E).Term " content " according to the present invention should preferably represent：It matrix and includes
Object forms different phases in heterophasic propylene copolymers (RAHECO), and the content is for example such as electric by high resolution microscope
Sub- microscope or atomic force microscope are as it can be seen that visible by dynamic mechanics heat analysis (DMTA).It, can particularly in DMTA
To identify the presence of heterogeneous structure by the presence of at least two different glass transition temperatures.
Preferably, heterophasic propylene copolymers (RAHECO) according to the present invention only include propylene-C4~C12Alpha-olefin copolymer
Object (C-PP) and elastomeric propylene copolymers (EC) are as polymers compositions.In other words, heterophasic propylene copolymers (RAHECO) can
With comprising other additives, but based on total heterophasic propylene copolymers (RAHECO), it includes other polymer amount not
More than 5.0wt%, more preferably no more than 3.0wt%, such as no more than 1.0wt%.It can another kind so existing for low content
Polymer is polyethylene, is the side reaction product by preparing heterophasic propylene copolymers (RAHECO) and acquisition.Therefore, it is especially excellent
Selection of land, heterophasic propylene copolymers of the invention (RAHECO) only contain propylene-C4~C12Alpha olefin copolymer (C-PP), elasticity third
The optional polyethylene of alkene copolymer (EC) and content as described in this paragraph.
Heterophasic propylene copolymers (RAHECO) according to the present invention are characterized in appropriate melt flow rate (MFR).Therefore, it is more
The melt flow rate (MFR) MFR of phase propylene copolymer (RAHECO)2(230 DEG C) in the range of 2.5~200.0g/10min, preferably
In the range of 5.0~100.0g/10min, more preferably in the range of 8.0~80.0g/10min, such as 8.0~
In the range of 50.0g/10min.
Preferably, it is desirable that heterophasic propylene copolymers (RAHECO) are thermo-mechanical robusts.It is therefore preferred that heterophasic propylene
Copolymer (RAHECO) has the significant melting temperature for being showed more than 50% total melting enthalpy, is at least 135 DEG C, more preferably exists
In the range of 137~155 DEG C, more preferably in the range of 139~150 DEG C.
Preferably, the crystallization temperature Tc of heterophasic propylene copolymers (RAHECO) is at most 105 DEG C (if without α-nucleation),
And the crystallization temperature Tc of heterophasic propylene copolymers (RAHECO) is at least 110 DEG C (if through α-nucleation).
As described above, heterophasic propylene copolymers (RAHECO) (are dispersed in the elastomeric propylene copolymers in matrix (M)
(EC)) heterogeneous structure can be identified by the presence of at least two different glass transition temperatures.Higher first
Glass transition temperature (Tg (1)) represents matrix (M), i.e. propylene-C4~C12Alpha olefin copolymer (C-PP), and relatively low second
The elastomeric propylene copolymers (E) of glass transition temperature (Tg (2)) reflection heterophasic propylene copolymers (RAHECO).
Therefore, heterophasic propylene copolymers (RAHECO) according to the present invention have the first glass transition temperature Tg (1) and
Second glass transition temperature Tg (2), wherein, first glass transition temperature Tg (1) is higher than the second glass transition temperature
Spend Tg (2), it is preferable that the difference between the first glass transition temperature Tg (1) and the second glass transition temperature Tg (2) is extremely
It is 20 DEG C few.It is more preferred still that the difference between the first glass transition temperature Tg (1) and the second glass transition temperature Tg (2)
It it is at least 24 DEG C, even more preferably from the range of 20~45 DEG C, even more preferably from the range of 24~40 DEG C.Preferably, first
Glass transition temperature Tg (1) is in the range of -5~+12 DEG C and/or the second glass transition temperature Tg (2) is -45~-25
In the range of DEG C.
Preferably, the second glass transition temperature Tg (2) is less than or equal to -25 DEG C, more preferably at -45 DEG C to being less than or wait
In the range of -25 DEG C, even more preferably from the range of -40~-28 DEG C.
It is further preferred that additionally, the first vitrifying of heterophasic propylene copolymers (RAHECO) according to the present invention turns
Temperature Tg (1) (matrix (M) for representing heterophasic propylene copolymers (RAHECO)) is in the range of -5~+12 DEG C, more preferably 0
In the range of~+10 DEG C, such as in the range of+2~+8 DEG C.
Preferably, heterophasic propylene copolymers (RAHECO) according to the present invention are through α-nucleation, i.e., comprising α-nucleating agent.More
Preferably, heterophasic propylene copolymers of the invention (RAHECO) are without nucleating agent.If there is α-nucleating agent, then α-nucleating agent
It is preferably chosen from group constituted by the following substances：
(i) unary carboxylation and polycarboxylate, such as sodium benzoate or p t butylbenzoic acid aluminium；And
(ii) dibenzyl sorbitol (such as 1,3:2,4 dibenzyl sorbitols) and C1-C8Alkyl-substituted two benzal
Base glucitol derivative, such as methyldibenzylidene sorbierite, ethyl dibenzyl sorbitol or dimethyldibenzylidenesorbitol
(such as 1,3:2,4 two (methylbenzilidene) sorbierites) or promise Buddhist nun alcohol (nonitol) derivative for being substituted, such as 1,2,3- tri-
Deoxy -4,6:Bis--the O- of 5,7- [(4- propyl phenyl) methylene]-Nuo Ni alcohol；And
(iii) di-phosphate ester salt, such as 2,2'- di-2-ethylhexylphosphine oxide (4,6- di-tert-butyl-phenyl) sodium phosphate or hydroxyl-bis- [2,
2'- methylene-bis- (4,6- di-tert-butyl-phenyls) phosphoric acid] aluminium；And
(iv) vinyl cycloalkane polymer and vinyl alkane polymers (in more detail as described below)；And
(v) its mixture.
The additive is usually commercially available, and for example such as the " plastic additive handbook (Plastic of Hans Zweifel
Additives Handbook) ", described in the 2009, the 6th edition (page 967~990).
The α of heterophasic propylene copolymers (RAHECO)-nucleation agent content preferably up to 5.0wt%.In preferred embodiment
In, heterophasic propylene copolymers (RAHECO) are containing α-nucleating agent no more than 3000ppm, more preferable 1~2000ppm, particularly,
α-the nucleating agent is selected from group constituted by the following substances：Dibenzyl sorbitol (such as 1,3：2,4 dibenzyl sorbitols)；
Dibenzalsorbierite derivatives, preferably dimethyldibenzylidenesorbitol are (for example, 1,3：2,4 two (methylbenzilidene) sorbs
Alcohol)；Or the promise Buddhist nun's 01 derivatives being substituted, such as 1,2,3- tri- deoxies -4,6：[(4- propyl phenyl) is sub- by 5,7- bis--O-
Methyl] promise Buddhist nun's alcohol；Vinyl cycloalkane polymer；Vinyl alkane polymers；And its mixture.
In a preferred embodiment, heterophasic propylene copolymers (RAHECO) containing vinyl cycloalkane polymer (such as
Vinyl cyclohexane (VCH) polymer) and/or vinyl alkane polymers as preferred α-nucleating agent.Preferably, in this reality
It applies in mode, propylene copolymer contains vinyl cycloalkane polymer (such as vinyl cyclohexane (VCH) polymer) and/or second
Alkenyl alkane polymer preferably comprises vinyl cyclohexane (VCH).It is highly preferred that in heterophasic propylene copolymers (RAHECO),
It is the amount of vinyl cycloalkane polymer (such as vinyl cyclohexane (VCH) polymer) and/or vinyl alkane polymers, more excellent
Select the amount of vinyl cyclohexane (VCH) polymer no more than 500ppm, more preferably 1~200ppm, most preferably 5~
100ppm。
α-nucleating agent can be introduced into as masterbatch.Optionally, some the α-nucleating agents limited in the present invention may be used also
To be introduced by BNT technologies.
α-nucleating agent can be introduced heterophasic propylene copolymers (RAHECO), such as at heterophasic propylene copolymers (RAHECO)
Polymerization process during；Or α-nucleating agent can be mixed into together with such as carrier polymer more in the form of masterbatch (MB)
Phase propylene copolymer (RAHECO).
In the case of masterbatch (MB) mixed embodiment, the weight (100wt%) based on masterbatch (MB), masterbatch (MB)
Containing no more than 500ppm, more preferable 1~200ppm, α-nucleating agent even more preferably from 5~100ppm, as described above or following institute
Ground is stated, which is preferably polymerized alpha-nucleating agent, most preferably vinyl cycloalkane polymer (such as vinyl cyclohexane
(VCH) polymer) and/or vinyl alkane polymers, optimal ethylene butylcyclohexane (VCH) polymer.In the present embodiment,
It is highly preferred that the total amount based on heterophasic propylene copolymers (RAHECO), the amount of the masterbatch (MB) is more excellent no more than 10.0wt%
Choosing is not more than 5.0wt%, most preferably no greater than 3.5wt%, wherein, the amount of masterbatch (MB) is preferably 1.5~3.5wt%.It is optimal
Selection of land, masterbatch (MB) are made of comprising following substances, preferably following substances：Third be nucleated according to BNT- technologies known in the art
The homopolymer or copolymer of alkene, preferably homopolymer.About BNT technologies, with reference to international application WO 99/24478, WO 99/
24479, particularly WO 00/68315.
At another preferred aspect, heterophasic propylene copolymers of the invention (RAHECO) have：
A) it is at least 500MPa according to the ISO 527-1 stretch moduluses measured at 23 DEG C, more preferably in 500~900MPa
In the range of, even more preferably from the range of 520~800MPa；
And/or
B) 3.0wt% is less than according to the hexane solubles content that FDA methods measure in 100 μm of casting films, more preferably existed
More than 0.8wt% in the range of being less than 3.0wt%, even more preferably from the range of 1.0~2.8wt%.
Other than propylene, heterophasic propylene copolymers (RAHECO) are also comprising other comonomers.It is therefore preferred that
The total comonomer content of heterophasic propylene copolymers (RAHECO) in the range of 12.0~35.0wt%, more preferably 15.0~
In the range of 30.0wt%, even more preferably from the range in the range of 18.0~28.0wt%, such as in 19.0~25.0wt%
It is interior.
As described above, and as detailed below, heterophasic propylene copolymers (RAHECO) include：Matrix (M) (i.e. propylene-C4
~C12Alpha olefin copolymer (C-PP)) and elastomeric propylene copolymers (EC) (it includes from propylene and at least list of ethylene
Member).Therefore, heterophasic propylene copolymers according to the present invention (RAHECO) are interpreted as polypropylene, it includes from following object
The unit of matter is preferably made of the unit for being derived from following substance：
(a) propylene,
(b) ethylene,
And
(c)C4~C12Alpha-olefin, preferably C4~C8Alpha-olefin, it is more preferably at least a kind of, such as a kind of to be selected from by following object
Texture into group alpha-olefin：1- butylene, 1- amylenes, 1- alkene, 1- heptene and 1- octenes, it is still more preferably at least a kind of, such as
A kind of alpha-olefin selected from group constituted by the following substances：1- butylene, 1- alkene and 1- octenes, even more preferably from 1- butylene and/
Or 1- alkene, such as 1- alkene.
Therefore, when the total comonomer content that heterophasic propylene copolymers (RAHECO) are described in detail, refer to be originated from ethylene and C4
~C12Alpha-olefin, more preferably from the total of ethylene and 1- butylene and/or the 1- unit of alkene (such as from ethylene and 1- alkene)
Amount (total weight for being based on heterophasic propylene copolymers (RAHECO)).
Preferably, heterophasic propylene copolymers (RAHECO) according to the present invention preferably satisfy inequality (I), more preferably meet
Inequality (Ia), even more preferably from meet inequality (Ib), even more preferably from meeting inequality (Ic)；
Wherein,
C2 (total) is the ethylene contents [wt%] of heterophasic propylene copolymers (RAHECO)；
Cx (total) is the C of heterophasic propylene copolymers (RAHECO)4~C12Alpha-olefin content, preferably 1- butylene and/or 1- are
Alkene content [wt%].
It is therefore preferred that the ethylene contents of heterophasic propylene copolymers (RAHECO) are in the range of 12.0~33.0wt%,
More preferably in the range of 15.0~30.0wt%, even more preferably from the range of 16.0~25.0wt%.
Additionally or alternatively, relative ethylene content, it is preferable that the C of heterophasic propylene copolymers (RAHECO)4~C12α-alkene
Alkene content in the range of 0.5~6.0wt%, more preferably exists alkene content such as 1- by hydrocarbon content, preferably 1- butylene and/or 1-
In the range of 1.0~5.0wt%, even more preferably from the range of 1.2~4.5wt%, even more preferably from 1.5~4.0wt%'s
In the range of.
Heterophasic propylene copolymers (RAHECO) are according to (25 DEG C) the cold soluble matter of dimethylbenzene (XCS) grades measured of ISO 16152
Divide in 10.0wt% in the range of being less than or equal to 40.0wt%, preferably in the range of 12.0~30.0wt%, more preferably
In the range of 12.0~25.0wt%, even more preferably from the range of 12.0~23.0wt%.
Remainder is the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO).Therefore, multiphase third
Dimethylbenzene cold insoluble matter (XCI) fraction of alkene copolymer (RAHECO) is in the range less than or equal to 60.0wt% to 90.0wt%
It is interior, preferably in the range of 70.0~88.0wt%, more preferably in the range of 75.0~88.0wt%, even more preferably from 77.0
In the range of~88.0wt%.
The total comonomer content of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO), i.e. second
Alkene and C4~C12The total content of alpha-olefin is in the range of 3.0~12.0wt%, more preferably in the range of 4.0~10.0wt%
It is interior, even more preferably from the range of 5.0~9.5wt%, even more preferably from the range of 5.5~9.0wt%.
Comonomer present in the cold insoluble matter of dimethylbenzene (XCI) fraction is those comonomers as described above, i.e.,
(i) ethylene
And
(ii)C4~C12Alpha-olefin, preferably C4~C8Alpha-olefin, it is more preferably at least a kind of, such as a kind of to be selected from by following
The alpha-olefin for the group that substance is formed：1- butylene, 1- amylenes, 1- alkene, 1- heptene and 1- octenes, still more preferably at least a kind of, ratio
Such as a kind of alpha-olefin selected from group constituted by the following substances：1- butylene, 1- alkene and 1- octenes, even more preferably from 1- butylene
And/or 1- alkene, such as 1- alkene.
Preferably, the ethylene contents of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO) are 2.0
In the range of~11.0wt%, more preferably in the range of 3.0~9.0wt%, even more preferably from the range in 3.5~8.0wt%
It is interior, even more preferably from the range of 4.0~7.0wt%, such as in the range of 4.5~6.5wt%.
Preferably, the C of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)4~C12Alpha-olefin
Content (such as 1- butene contents and/or 1- alkene content) is in the range of 0.5~6.0wt%.More preferably 1.0~
In the range of 5.5wt%, even more preferably from the range of 1.5~5.0wt%, even more preferably from the range in 1.8~4.5wt%
It is interior, such as in the range of 2.0~4.0wt%.
It is therefore especially preferred that ground, heterophasic propylene copolymers (RAHECO) meet inequality (II), more preferably meet inequality
(IIa), even more preferably from meeting inequality (IIb), even more preferably from meeting inequality (IIc)；
Wherein,
C2 (XCI) is the ethylene contents of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
Cx (XCI) is the C of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)4~C12α-alkene
Hydrocarbon content [wt%], preferably 1- alkene content [wt%].
It is particularly preferred below about the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO).
Preferably, the cold soluble matter fraction (XCS) of the dimethylbenzene of heterophasic propylene copolymers (RAHECO) is according to ISO1628/1
The inherent viscosity (IV) that (at 135 DEG C, in naphthalane) measures is at least 1.2dl/g, more preferably in the range of 1.2~2.5dl/g,
More preferably in the range of 1.4~2.2dl/g, even more preferably from the range of 1.5~2.0dl/g.
Furthermore it is preferred that total copolymerization of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO) is single
Body content and/or ethylene contents are in the range of 30.0~90.0wt%, even more preferably from the range of 50.0~90.0wt%,
Even more preferably from the range of 60.0~90.0wt%, such as in the range of 70.0~85.0wt%.The cold soluble matter of dimethylbenzene
(XCS) comonomer present in fraction is those comonomers as described above, i.e.,
(iii) ethylene
And optionally,
(iv)C4~C12Alpha-olefin, preferably C4~C8Alpha-olefin, it is more preferably at least a kind of, such as a kind of to be selected from by following
The alpha-olefin for the group that substance is formed：1- butylene, 1- amylenes, 1- alkene, 1- heptene and 1- octenes, still more preferably at least a kind of, ratio
Such as a kind of alpha-olefin selected from group constituted by the following substances：1- butylene, 1- alkene and 1- octenes, even more preferably from 1- butylene
And/or 1- alkene, such as 1- alkene.
Furthermore it is preferred that heterophasic propylene copolymers (RAHECO) according to the present invention meet inequality (III), more preferably
Meet inequality (IIIa), even more preferably from meeting inequality (IIIb),
Wherein,
C (XCS) is that the total comonomer of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO) contains
It measures [wt%]；
C (total) is the total comonomer content [wt%] of heterophasic propylene copolymers (RAHECO).
Additionally or alternatively, with respect to inequality (III), it is preferable that heterophasic propylene copolymers (RAHECO) satisfaction differs
Formula (IV) more preferably meets inequality (IVa), even more preferably from meeting inequality (IVb), even more preferably from meeting inequality (IVc),
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C2 (total) is the ethylene contents [wt%] of heterophasic propylene copolymers (RAHECO).
Furthermore it is preferred that heterophasic propylene copolymers (RAHECO) meet inequality (V), more preferably meet inequality (Va),
Even more preferably from meeting inequality (Vb),
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C (XCI) is that the total comonomer of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO) contains
It measures [wt%], i.e. ethylene contents and C4~C12Alpha-olefin content.
In a specific preferred embodiment, heterophasic propylene copolymers (RAHECO) meet inequality (VI), more
Inequality (VIa) is preferably satisfied, even more preferably from meeting inequality (VIb), even more preferably from meeting inequality (VIc),
Wherein,
C2 (XCS) is the ethylene contents of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO)
[wt%]；
C2 (XCI) is the ethylene contents of the cold insoluble matter of dimethylbenzene (XCI) fraction of heterophasic propylene copolymers (RAHECO)
[wt%].
Finally, it is preferable that heterophasic propylene copolymers (RAHECO) according to the present invention preferably satisfy inequality (VIII), more
Inequality (VIIIa) is preferably satisfied, even more preferably from meeting inequality (VIIIb),
Wherein,
C (XCS) is the total comonomer content of heterophasic propylene copolymers (RAHECO), i.e. ethylene contents and C4~C12α-alkene
Hydrocarbon content [wt%]；
XCS is the content [wt%] of the cold soluble matter of dimethylbenzene (XCS) fraction of heterophasic propylene copolymers (RAHECO).
In addition to α-nucleating agent, heterophasic propylene copolymers (RAHECO) as described in the present invention can also be contained, preferably contain
There is an at most additive of 5.0wt%, for example antioxidant, acid scavenger, ultra-violet stabilizer and processing aid are (such as refreshing
Lubrication prescription and anti-blocking agent).Preferably, additive level (not including α-nucleating agent) is less than 3.0wt%, such as less than 1.0wt%.
As described above, heterophasic propylene copolymers (RAHECO) include matrix (M) (i.e. propylene-C4~C12Alpha olefin copolymer
(C-PP)) and the elastomeric propylene copolymers (EC) that are scattered in the matrix (M) are as key component.Therefore, heterophasic propylene is common
Polymers (RAHECO) can be further defined by these single components, that is, pass through propylene-C4~C12Alpha olefin copolymer
(C-PP) it is defined with elastomeric propylene copolymers (EC).
Therefore, propylene-C according to the present invention4~C12Alpha olefin copolymer (C-PP) includes the list from following substance
Member：(i) propylene；And (ii) is at least one, preferably a kind of C4~C12Alpha-olefin, such as 1- alkene.Therefore, propylene-C4~C12
Alpha olefin copolymer (C-PP) is formed comprising following substances, by following substances：Copolymerizable monomer, i.e. C with propylene4~C12α-alkene
Hydrocarbon, particularly C4~C8Alpha-olefin, such as C4~C6Alpha-olefin, such as 1- butylene and/or 1- alkene.Preferably, according to the present invention
Propylene-C4~C12Alpha olefin copolymer (C-PP) is comprising the monomer copolymerizable with propylene, especially by the list copolymerizable with propylene
Body forms, and free 1- butylene, the 1- group that alkene, 1- octenes are formed should be carried out with the copolymerizable monomer of propylene.More specifically, this hair
Bright propylene-C4~C12Alpha olefin copolymer (C-PP) also includes other than comprising propylene and has been originated from 1- butylene and/or 1-
The unit of alkene, preferably 1- alkene.In a preferred embodiment, propylene-C4~C12Alpha olefin copolymer (C-PP) only includes source
From in the unit of propylene and 1- alkene, i.e., it is propylene -1- alkene copolymer (C6-PP)。
Propylene-C4~C12The co-monomer content of alpha olefin copolymer (C-PP), preferably C4~C12It is alpha-olefin content, more excellent
Select 1- butylene and/or 1- alkene content such as 1- alkene content in the range of 1.5~9.0wt%, even more preferably from 2.0~
In the range of 6.0wt%, even more preferably from the range of 2.5~5.0wt%.
Preferably, propylene-C4~C12The melt flow rate (MFR) MFR of alpha olefin copolymer (C-PP)2(230 DEG C) 5.0~
In the range of 100.0g/10min, preferably in the range of 10.0~80.0g/10min, more preferably in 20.0~60.0g/
In the range of 10min.
Propylene-C4~C12Alpha olefin copolymer (C-PP) is according to (25 DEG C) the cold soluble matter of dimethylbenzene measured of ISO 16152
(XCS) fraction is preferably smaller than 10.0wt%, more preferably in 0.2wt% in the range of being less than or equal to 7.0wt%, even more preferably from
In the range of 0.8~5.0wt%, more preferably in the range of 0.8~2.5wt%.
Preferably, propylene copolymer (R-PP) includes at least two polymers compositions, such as two or three of polymer group
Point；At least one of they are propylene-C4~C12Alpha olefin copolymer.It is further preferred that propylene-C4~C12Alpha-olefin copolymer
Object (C-PP) is made of comprising following substances, preferably following substances：First polypropylene component (PP1) and the second propylene-C4~C12
Alpha olefin copolymer component (C-PP2).It is particularly preferred that propylene-C4~C12Alpha olefin copolymer (C-PP) comprising following substances,
It is preferred that it is made of following substances：First polypropylene component (PP1) and the second propylene-C4~C12Alpha olefin copolymer component (C-
PP2), wherein, the co-monomer content at most 4.0wt% in the first polypropylene component (PP1).
First polypropylene component (PP1) such as the first propylene-C4~C12Alpha olefin copolymer component (C-PP1) and the two the third
Alkene-C4~C12Model of the weight ratio [(PP1)/(C-PP2)] 30/70~70/30 between alpha olefin copolymer component (C-PP2)
In enclosing, more preferably in the range of 35/65~65/35, such as in the range of 40/60~55/45.
Preferably, the first polypropylene component (PP1) such as the first propylene-C4~C12Alpha olefin copolymer component (C-PP1)
It is the thin component of comonomer, such as C4~C12The thin component of alpha-olefin；And the second propylene-C4~C12Alpha olefin copolymer component
(C-PP2) it is comonomer enriched composition, such as C4~C12Alpha-olefin enriched composition.Therefore, in a preferred embodiment
In, propylene-C4~C12Co-monomer content such as C in alpha olefin copolymer (C-PP)4~C12Alpha-olefin content [wt%] is high
In the first propylene-C4~C12Those in alpha olefin copolymer component (C-PP1).
It is therefore preferred that the first polypropylene component (PP1) such as the first propylene-C4~C12Alpha olefin copolymer component (C-
PP1) there is rather low co-monomer content, such as with rather low C4~C12Alpha-olefin content.
It is therefore preferred that the first polypropylene component (PP1) of heterophasic propylene copolymers (RAHECO) is：
(a) propylene homopolymer component (H-PP1)；
Or
(b) the first propylene-C4~C12Alpha olefin copolymer component (C-PP1), it is preferable that first propylene-
C4~C12The C of alpha olefin copolymer component (C-PP1)4~C12Alpha-olefin content is in the range of 0.5~4.0wt%
It is interior.
It is particularly preferred that the first polypropylene component (PP1) is the first propylene-C being defined herein4~C12Alpha-olefin copolymer
Object component (C-PP1).
The term Noblen used in the present invention, such as the first Noblen (component) (H-PP1) are related to one kind
Polypropylene, the polypropylene are substantially made of propylene units, i.e., by being more than the 99.0mol% such as at least propylene of 99.5mol%
Unit is formed, and is formed even more preferably from by at least propylene units of 99.7mol%.In a preferred embodiment, only propylene homo
Propylene units in object, such as the first Noblen (component) (H-PP1) is detectable.
It is the first propylene-C in the first polypropylene component (PP1)4~C12The situation of alpha olefin copolymer component (C-PP1)
Under, it includes the units from following substance：(i) propylene；And (ii) is at least one, preferably a kind of C4~C12Alpha-olefin,
Such as 1- alkene.Therefore, the first propylene-C4~C12Alpha olefin copolymer component (C-PP1) comprising following substances, by following substances
Composition：Copolymerizable monomer, i.e. C with propylene4~C12Alpha-olefin, particularly C4~C8Alpha-olefin, such as C4~C6Alpha-olefin, example
Such as 1- butylene and/or 1- alkene.Preferably, the first propylene-C according to the present invention4~C12Alpha olefin copolymer component (C-PP1)
Comprising the monomer copolymerizable with propylene, particularly by the monomer composition copolymerizable with propylene, should come with the copolymerizable monomer of propylene
Free 1- butylene, the 1- group that alkene, 1- octenes are formed.More specifically, the first propylene-C of the invention4~C12Alpha-olefin copolymer
Object component (C-PP1) also includes the unit from 1- butylene and/or 1- alkene, preferably 1- alkene other than comprising propylene.
In preferred embodiment, the first propylene-C4~C12Alpha olefin copolymer component (C-PP1) only includes and has been derived from propylene and 1-
The unit of alkene, i.e., it is the first propylene -1- alkene copolymer component (C6-PP1)。
First propylene-C4~C12The co-monomer content of alpha olefin copolymer component (C-PP1), preferably C4~C12Alpha-olefin
Content, more preferable 1- butylene and/or 1- alkene content such as 1- alkene contents, it is also more excellent in the range of 0.5~4.0wt%
It is selected in the range of 0.5~3.5wt%, even more preferably from the range of 0.7~3.0wt%.
It is further preferred that the first polypropylene component (PP1) (such as the first propylene-C4~C12Alpha olefin copolymer component
(C-PP1)) amount of the cold soluble matter of dimethylbenzene (XCS) fraction is less than or equal to 4.0wt%, more preferably 0.5~3.5wt%'s
In the range of, even more preferably from the range of 0.8~2.5wt%.
Preferably, the first polypropylene component (PP1) such as the first propylene-C4~C12Alpha olefin copolymer component (C-PP1)
Melt flow rate (MFR) MFR2(230 DEG C) in the range of 5.0~100.0g/10min, preferably in 10.0~80.0g/10min
In the range of, more preferably in the range of 20.0~60.0g/10min.
Propylene-C4~C12Second component of alpha olefin copolymer (C-PP) is copolymer component, i.e. the second propylene-C4~C12
Alpha olefin copolymer component (C-PP2) compared to the first polypropylene component (PP1), has higher co-monomer content, excellent
Select higher C4~C12Alpha-olefin content, more preferable higher 1- butylene and/or 1- alkene contents, for example alkene contains higher 1-
Amount.
It is particularly preferred that propylene-C4~C12Alpha olefin copolymer (C-PP) and the first polypropylene component (PP1) (such as
One propylene-C4~C12Alpha olefin copolymer component (C-PP1)) between in co-monomer content (preferably C4~C12Alpha-olefin content,
More preferable 1- butylene and/or 1- alkene content, such as 1- alkene contents) on difference [(C-PP)-(PP1)] difference at least
1.5wt%；More preferable 1.5~6.0wt%, even more preferably from 1.5~4.0wt%, even more preferably from 1.8~3.5wt%.
It is therefore preferred that the second propylene-C4~C12The co-monomer content of alpha olefin copolymer component (C-PP2) is (preferably
C4~C12Alpha-olefin content, more preferable 1- butylene and/or 1- alkene content, such as 1- alkene contents) it is greater than or equal to
2.0wt%, more preferably in the range of 2.0~15.0wt%, such as 2.0~10.0wt%, even more preferably from 3.0~
In the range of 8.0wt%.
Therefore, it is further preferred that the second propylene-C4~C12Alpha olefin copolymer component (C-PP2) and the first polypropylene
Component (PP1) (such as the first propylene-C4~C12Alpha olefin copolymer component (C-PP1)) between co-monomer content (preferably
C4~C12Alpha-olefin content, more preferable 1- butylene and/or 1- alkene content, such as 1- alkene contents) difference [(C-PP2)-
(PP1)] it is at least 2.5wt%, more preferable 2.5~10.0wt%, such as 3.0~10.0wt%, even more preferably from 3.0~
8.0wt%, even more preferably from 3.0~6.0wt%.
Second propylene-C4~C12Alpha olefin copolymer component (C-PP2) includes the unit from following substance：(i) third
Alkene；And (ii) is at least one, preferably a kind of C4~C12Alpha-olefin, such as 1- alkene.Therefore, the second propylene-C4~C12α-alkene
Hydrocarbon copolymer component (C-PP2) is formed comprising following substances, by following substances：Copolymerizable monomer, i.e. C with propylene4~C12α-
Alkene, particularly C4~C8Alpha-olefin, such as C4~C6Alpha-olefin, such as 1- butylene and/or 1- alkene.Preferably, according to this hair
The second bright propylene-C4~C12Alpha olefin copolymer component (C-PP2) is comprising the monomer copolymerizable with propylene, particularly by with third
The copolymerizable monomer composition of alkene should carry out free 1- butylene, the 1- group that alkene, 1- octenes are formed with the copolymerizable monomer of propylene.More
Specifically, the second propylene-C of the present invention4~C12Alpha olefin copolymer component (C-PP2) is also wrapped other than comprising propylene
Containing the unit from 1- butylene and/or 1- alkene, preferably 1- alkene.In a preferred embodiment, the second propylene-C4~C12α-
Olefin copolymer component (C-PP2) only includes the unit from propylene and 1- alkene, i.e., its for the second propylene -1-, alkene is copolymerized
Object component (C6-PP2)。
In a specific preferred embodiment, propylene-C4~C12Alpha olefin copolymer (C-PP) comprising following substances,
It is preferred that it is made of following substances：First propylene-C4~C12Alpha olefin copolymer component (C-PP1) and the second propylene-C4~C12α-
Olefin copolymer component (C-PP2), wherein, this two component is formed comprising following substances, by following substances：From propylene and
At least one C4~C12The unit of alpha-olefin is more preferably derived from propylene and a kind of C4~C12The unit of alpha-olefin, even more preferably from
From propylene and the 1- unit of alkene or unit from propylene and 1- butylene.In a kind of specific preferred embodiment
In, propylene-C4~C12Alpha olefin copolymer (C-PP) is made of comprising following substances, preferably following substances：First propylene-C4~
C12Alpha olefin copolymer component (C-PP1) and the second propylene-C4~C12Alpha olefin copolymer component (C-PP2), wherein, this two groups
Divide comprising following substances, be only made of following substances：Propylene and 1- alkene.
Preferably, matrix (M) (i.e. propylene-C4~C12Alpha olefin copolymer (C-PP)) and elastomeric propylene copolymers (EC) it
Between weight ratio in the range of 15/1~2/1, more preferably in the range of 10/1~5/2, even more preferably from 8/1~3/1
In the range of.
Therefore, in one preferred embodiment, the total weight based on heterophasic propylene copolymers (RAHECO), multiphase third
Alkene copolymer (RAHECO) preferably comprises matrix (M) (i.e. propylene-C of 65~95wt%, more preferable 70~90wt%4~C12α-
Olefin copolymer (C-PP)).
In addition, the total weight based on heterophasic propylene copolymers (RAHECO), heterophasic propylene copolymers (RAHECO) are preferred to be wrapped
Elastomeric propylene copolymers (EC) containing 5~35wt%, more preferable 10~30wt%.
It is therefore preferred that the total weight based on heterophasic propylene copolymers (RAHECO), heterophasic propylene copolymers (RAHECO)
It preferably comprises following substances, be more preferably made of following substances：65~95wt%, more preferable 70~90wt% matrix (M) (i.e.
Propylene-C4~C12Alpha olefin copolymer (C-PP))；And 5~35wt%, the elastomeric propylene copolymers of more preferable 10~30wt%
(EC)。
Therefore, another component of heterophasic propylene copolymers (RAHECO) is that the elastomeric propylene being dispersed in matrix (M) is total to
Polymers (EC).Elastomeric propylene copolymers (EC) include the unit from following substance：
(i) propylene and
(ii) ethylene and optional at least one C4~C12Alpha-olefin.
Therefore, elastomeric propylene copolymers (EC) include the monomer copolymerizable with propylene, i.e. ethylene and optional at least one
C4~C12Alpha-olefin (such as a kind of C4~C12Alpha-olefin), particularly ethylene and optionally a kind of C4~C6Alpha-olefin is (for example, 1-
Butylene and/or 1- alkene).Preferably, elastomeric propylene copolymers (EC) are formed comprising following substances, particularly by following substances：
Propylene, ethylene and optional 1- butylene and 1- alkene.More specifically, other than propylene, elastomeric propylene copolymers (EC)
Also include the unit from ethylene and optional 1- alkene.Therefore, in one embodiment, elastomeric propylene copolymers (EC)
The unit from ethylene and propylene is only included, i.e., it is ethylene-propylene rubber (EPR).
Co-monomer content (optimal ethylene and the C of elastomeric propylene copolymers (EC)4~C12Alpha-olefin content, more preferable second
Alkene content) in the range of 40.0~95.0wt%, even more preferably from the range of 40.0~90.0wt%, even more preferably from
In the range of 50.0~90.0wt%, such as in the range of 70.0~90.0wt.
The present invention is directed not only to the heterophasic propylene copolymers (RAHECO) of the present invention, further relates to product, is preferably directed to be selected from
In the product of group being made of (medicine) bag, food packaging articles, film such as non-oriented film and bottle.Therefore, another
In embodiment, the present invention relates to a kind of product, more particularly to a kind of product selected from group constituted by the following substances：(doctor
Medicine) bag, food packaging articles, film such as non-oriented film (i.e. casting films or blown film, such as air cooling blown film) and bottle
Son it includes at least 70.0wt%, preferably comprises at least 80.0wt%, more preferably comprising at least 90.0wt%, even more preferably from packet
Containing at least 95.0wt%, even more preferably from the heterophasic propylene copolymers (RAHECO) of the present invention comprising at least 99.0wt%.
There are a difference (for example, see polypropylene handbook (polypropylene between non-oriented film and alignment films
Handbook), Nello Pasquini, the second edition, Hanser).Alignment films are usually a monoaxially oriented film or Biaxially oriented film, and
Non-oriented film is then casting films or blown film.Therefore, non-oriented film be not as alignment films carry out machine direction and/
Or it is consumingly stretched on horizontal direction.Therefore, non-oriented film according to the present invention is not a monoaxially oriented film or biaxial orientation
Film.Preferably, non-oriented film according to the present invention is blown film or casting films.
In a specific embodiment, non-oriented film is casting films or through air cooled blown film.
Preferably, the thickness of non-oriented film is 10~1000 μm, more preferably 20~700 μm, such as 40~500 μm.
The invention further relates to heterophasic propylene copolymers (RAHECO) in system of the manufacture selected from group constituted by the following substances
The purposes of product：(medicine) bag, food packing system, film such as non-oriented film (i.e. casting films or blown film, such as cold through air
But blown film or the blown film through water quenching) and bottle.
Preferably, heterophasic propylene copolymers of the invention (RAHECO) are prepared in multistage process, the multistage
Process includes at least two reactors being connected in series with, and preferably comprises at least three reactors being connected in series with.
Therefore, heterophasic propylene copolymers (RAHECO) according to the present invention are made as follows：
(I) polypropylene and at least one C4~C12Alpha-olefin, preferably a kind of C4~C12Alpha-olefin, more preferable 1- butylene
And/or 1- alkene, such as 1- alkene, so as to form matrix (M) (i.e. propylene-C4~C12Alpha olefin copolymer (C-PP))；And
(II) then, in the gas phase, polypropylene and ethylene and optional at least one C4~C12Alpha-olefin, preferably
Propylene and ethylene, so as to form the elastomeric propylene copolymers (EC) being scattered in the matrix (M)；
Wherein it is preferred to step (I) and (II) both in the presence of identical unit point solid particle catalyst into
Row, unit point solid particle catalyst is preferably without outer carrier, the more preferably complex compound in (i) formula (I) as detailed below that includes
Catalyst in the presence of carry out.
Preferably, heterophasic propylene copolymers (RAHECO) are obtained by continuous polymerization, the continuous polymerization include with
Lower step：
(a) in the first reactor, polymerization (i) propylene and (ii) optional at least one C4~C12Alpha-olefin (preferably one
Kind C4~C12Alpha-olefin, more preferable 1- butylene and/or 1- alkene, such as 1- alkene), thus to obtain the first polypropylene component
Such as the first propylene-C (PP1),4~C12Alpha olefin copolymer component (C-PP1),
(b) by first polypropylene component (PP1), preferably described first propylene-C4~C12Alpha olefin copolymer component
(C-PP1) it is transferred in second reactor,
(c) in the second reactor, in the presence of the first polypropylene component (PP1), preferably in the first propylene-C4
~C12In the presence of alpha olefin copolymer component (C-PP1), polymerization (i) propylene and (ii) at least one C4~C12Alpha-olefin is (excellent
Select a kind of C4~C12Alpha-olefin, more preferable 1- butylene and/or 1- alkene, such as 1- alkene), obtain the second propylene-C4~C12α-
Olefin copolymer component (C-PP2), the first polypropylene component (PP1) (preferably described first propylene-C4~C12Alpha-olefin is total to
Copolymer component (C-PP1)) and the second propylene-C4~C12Alpha olefin copolymer component (C-PP2) formation matrix (M), i.e., third
Alkene-C4~C12Alpha olefin copolymer (C-PP),
(d) matrix (M) is transferred in third reactor,
(e) in the third reactor, in the presence of matrix (M), polypropylene and ethylene and it is optional at least
A kind of C4~C12Alpha-olefin (preferably propylene and ethylene) obtains elastomeric propylene copolymers (EC), the matrix (M) and the elasticity
Propylene copolymer (EC) forms heterophasic propylene copolymers (RAHECO),
Wherein it is preferred to the step carries out in the presence of identical unit point solid particle catalyst, unit point solid
Beaded catalyst is preferably without outer carrier, the more preferably presence in the catalyst of the complex compound comprising (i) formula (I) as detailed below
Lower progress.
For the preferred embodiment of heterophasic propylene copolymers (HECO), propylene-C4~C12Alpha olefin copolymer (C-
PP), the first polypropylene component (PP1) such as the first propylene-C4~C12Alpha olefin copolymer component (C-PP1), the second propylene-C4
~C12Alpha olefin copolymer component (C-PP2) and elastocopolymer (CE) refer to above-mentioned definition.
Term " continuous polymerization " represents, in the reactor that heterophasic propylene copolymers (HECO) are connected in series at least two
It prepares, for example is prepared in the reactor being connected in series at three.Therefore, method of the invention includes at least first reactor, the
Two reactors and optional third reactor.Term " polymerization " should represent that main polymerization occurs.Therefore, in method by three
In the case that polymer reactor is formed, following option is not precluded in this definition：Entire technique is included for example in pre-polymerization reactor
In prepolymerization step.Term " by ... form " it is only for closed manners for the viewpoint of main polymerisation method.
First reactor is preferably slurry reactor, and can be any continuous or simple agitation batch tank
Reactor or the loop reactor operated in ontology or slurry.Ontology refers to the polymerisation in reaction medium, packet
Monomer containing at least 60% (w/w).According to the present invention, slurry reactor is preferably (ontology) loop reactor.
Second reactor and third reactor are preferably gas-phase reactor.This gas-phase reactor can be that any machinery is mixed
Close reactor or fluidized-bed reactor.Preferably, gas-phase reactor includes the mechanical agitation stream that gas velocity is at least 0.2m/ seconds
Fluidized bed reactor.It is therefore preferred that gas-phase reactor is fluid bed-type of reactor, preferably there is the fluidisation of mechanical agitator
Bed-type reactor.
Therefore, in a preferred embodiment, first reactor is slurry reactor, such as loop reactor, and second
Reactor and third reactor are then gas-phase reactor (GPR).Therefore, for the present invention technique, using be connected in series with to
Few three polymer reactors, preferably three polymer reactors, i.e. slurry reactor such as loop reactor, the first gas-phase reactor
With the second gas-phase reactor.Optionally, before slurry reactor, pre-polymerization reactor is placed.
Preferred multistage process is such as Borealis A/S, and " loop-gas phase " technique of Denmark's exploitation (is known asTechnology), as described in following patent documents, such as such as EP 0 887 379, WO 92/12182, WO 2004/
000899th, described in WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.
Another suitable slurry-gas phase process is BasellTechnique.
Preferably, it in the method for the present invention for being used to prepare heterophasic propylene copolymers as described above (RAHECO), uses
It can be as follows in the condition of first reactor, that is, slurry reactor (such as loop reactor)：
Temperature is in the range of 50 DEG C~110 DEG C, preferably between 60 DEG C~100 DEG C, more preferably 65~95 DEG C it
Between.
Pressure is in the range of 20bar~80bar, preferably between 40bar~70bar,
Can hydrogen be added by the second to control molal weight in a known way.
Then, the reaction mixture of first reactor is transferred to second reactor, i.e. gas-phase reactor, wherein, condition
It is it is preferred that as follows：
Temperature is in the range of 50 DEG C~130 DEG C, preferably between 60 DEG C~100 DEG C；
Pressure is in the range of 5bar~50bar, preferably between 15bar~35bar；
Can hydrogen be added by the second to control molal weight in a known way.
Condition and second reactor in third reactor is similar.
Residence time in three reactors can be different.
In an embodiment for being used to prepare the method for heterophasic propylene copolymers (RAHECO), in bulk reaction device
Residence time in residence time, such as loop reactor in the range of 0.1~2.5 hour, such as 0.15~1.5 hour,
And the residence time in gas-phase reactor is usually 0.2~6.0 hour, such as 0.3~4.0 hour.
It optionally, in the first reactor, i.e., can known side in slurry reactor, such as in loop reactor
Formula is polymerize at supercritical conditions；And/or in gas-phase reactor, gathered with condensation mode (condensed mode)
It closes.
In the following, catalytic component will be defined in greater detail.Preferably, catalyst includes the complex compound of (i) formula (I)：
(i) transistion metal compound of formula (I)
Rn(Cp’)2MX2(I)
Wherein,
" M " be zirconium (Zr) or hafnium (Hf),
Each " X " independently is univalent anion σ-ligand,
Each " Cp ' " is cyclopentadienyl type organic ligand, independently selected from group constituted by the following substances：
Substituted cyclopentadienyl group, the indenyl of substitution, the tetrahydro indenyl of substitution and substituted or unsubstituted fluorenyl, institute
Organoligand coordination is stated in transition metal (M),
" R " is the divalent bridging group for connecting the organic ligand (Cp '),
" n " be 1 or 2, preferably 1 and
(ii) co-catalyst, it includes the compounds of the 13rd race's metal, such as Al compounds or boride.
In a specific embodiment, unit point solid particle catalyst is small according to the porosity that ASTM 4641 is measured
In 1.40mL/g；And/or unit point solid particle catalyst is less than 25m according to the surface area that ASTM D 3663 are measured2/g。
Preferably, the surface area of unit point solid particle catalyst is less than 15m2/ g, also preferably less than 10m2/ g, most preferably
Less than 5m2/ g (this is that minimum measure limits).Surface area according to the present invention is according to 3663 (N of ASTMD2) measure.
Alternatively or additionally, it is preferable that the porosity of unit point solid particle catalyst is less than 1.30mL/g, more excellent
Choosing is less than 1.00mL/g.Porosity is according to 4641 (N of ASTM2) be measured.In another preferred embodiment, when using
According to 4641 (N of ASTM2) used by method when being measured, porosity can not detect.
Further, in general, the average grain diameter of unit point solid particle catalyst is not more than 500 μm, i.e., preferably 2~
In 500 μ ms, more preferable 5~200 μm.It is particularly preferred that average grain diameter is less than 80 μm, even more preferably less than 70 μm.It is average
Preferably ranging from 5~70 μm or even 10~60 μm of grain size institute.
As described above, transition metal (M) is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
Throughout the specification, term " σ-ligand " understands in known manner, i.e., the base of metal is bonded to via σ keys
Group.Therefore, anion ligand " X " can independently be halogen or selected from group constituted by the following substances：R’、OR’、SiR’3、
OSiR’3、OSO2CF3、OCOR’、SR’、NR’2Or PR '2Group, wherein, R ' independently be hydrogen, linear chain or branch chain, it is cyclic annular or
The acyclic C of person1To C20Alkyl, C2To C20Alkenyl, C2To C20Alkynyl, C3To C12Cycloalkyl, C6To C20Aromatic radical, C7To C20Aralkyl
Base, C7To C20Alkylaryl, C8To C20Aralkenyl, wherein, R ' group optionally can belong to the 14th comprising more than one
The hetero atom of~16 races.In a preferred embodiment, anion ligand " X " is identical, and be halogen (such as Cl) or
Person's methyl or benzyl.
Preferred univalent anion ligand is halogen, particularly chlorine (Cl).
Substituted cyclopentadienyl-type ligands can have more than one taking selected from group constituted by the following substances
Dai Ji：Halogen, alkyl (such as C1To C20Alkyl, C2To C20Alkenyl, C2To C20Alkynyl, C3To C20Cycloalkyl, such as C1To C20Alkane
The C of base substitution5To C20Cycloalkyl, C6To C20Aromatic radical, C5To C20The C of cycloalkyl substitution1To C20(wherein, cycloalkyl is residual for alkyl
Base is by C1To C20Alkyl replace), C7To C20Aralkyl, C3To C12(it is miscellaneous containing 1,2,3 or 4 on loop section for cycloalkyl
Atom), C6To C20Heteroaryl perfume base, C1To C20Halogenated alkyl) ,-SiR "3、-SR”、-PR”2Or-NR "2, each R " independently is
Hydrogen or alkyl are (for example, C1To C20Alkyl, C1To C20Alkenyl, C2To C20Alkynyl, C3To C12Cycloalkyl or C6To C20Fragrance
Base)；Such as in-NR "2In the case of, two substituent Rs " can with nitrogen-atoms (wherein, two substituent Rs " connect with it
Connect) cyclization, such as five-membered ring or hexatomic ring.
Further, " R " of formula (I) is preferably the bridging of 1~4 atom, the atom independently be carbon (C), silicon (Si),
Germanium (Ge) or oxygen (O) atom, therefore each bridging atom can independently carry substituent group, such as C1To C20Alkyl, three (C1Extremely
C20Alkyl) silicyl, three (C1To C20Alkyl) siloxy, it is highly preferred that " R " is a kind of atom bridging, such as-
SiR”’2, wherein, each R " ' independently is C1To C20Alkyl, C2To C20Alkenyl, C2To C20Alkynyl, C3To C12Cycloalkyl, C6Extremely
C20Aromatic radical, alkylaryl or aralkyl or three (C1To C20Alkyl) silyl residues such as trimethyl silyl
Base-；Or two R " ' can be a part for the member ring systems for including Si bridging atoms.
In a preferred embodiment, transistion metal compound has formula (II)：
Wherein,
M is zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr),
X is ligand (wherein, σ-be bonded to metal " M "), preferably as described above for those described in formula (I),
It is preferred that chlorine (Cl) or methyl (CH3), particularly preferably the former,
R1It is same or different to each other, is preferably identical to each other, and selected from group constituted by the following substances：
The C of straight chain saturation1To C20The undersaturated C of alkyl, straight chain1To C20The C of alkyl, branch saturation1-C20Alkyl, branch
Undersaturated C1To C20Alkyl, C3To C20Cycloalkyl, C6To C20Aromatic radical, C7To C20Alkylaryl and C7To C20Aralkyl,
It optionally includes the hetero atom of the 14th~16 race of more than one periodic table (IUPAC),
Preferably, it is same or different to each other, is preferably identical to each other, and be C1To C10The alkyl of linear chain or branch chain；It is more excellent
Selection of land is same or different to each other, and is preferably identical to each other, and is C1To C6The alkyl of linear chain or branch chain,
R2-R6It is same or different to each other, and selected from group constituted by the following substances：Hydrogen；The C of straight chain saturation1-C20Alkane
The undersaturated C of base, straight chain1-C20The C of alkyl, branch saturation1-C20The undersaturated C of alkyl, branch1-C20Alkyl, C3-C20Cycloalkanes
Base, C6-C20Aromatic radical, C7To C20Alkylaryl and C7To C20Aralkyl optionally includes more than one periodic table
(IUPAC) hetero atom of the 14th~16 race,
Preferably, it is same or different to each other, and is C1To C10The alkyl of linear chain or branch chain；It is it is highly preferred that mutually the same
Or it is different, and be C1To C6The alkyl of linear chain or branch chain,
R7And R8It is same or different to each other, and selected from group constituted by the following substances：Hydrogen；The C of straight chain saturation1To C20
The undersaturated C of alkyl, straight chain1To C20The C of alkyl, branch saturation1To C20The undersaturated C of alkyl, branch1To C20Alkyl, C3Extremely
C20Cycloalkyl, C6To C20Aromatic radical, C7To C20Alkylaryl, C7To C20Aralkyl optionally includes the more than one period
The hetero atom of 14th~16 race of table (IUPAC)；SiR10 3；GeR10 3；OR10；SR10；And NR10 2,
Wherein,
R10Selected from group constituted by the following substances：The C of straight chain saturation1-C20The undersaturated C of alkyl, straight chain1To C20Alkane
The C of base, branch saturation1To C20The undersaturated C of alkyl, branch1To C20Alkyl, C3To C20Cycloalkyl, C6To C20Aromatic radical, C7Extremely
C20Alkylaryl and C7To C20Aralkyl, optionally the 14th~16 race comprising more than one periodic table (IUPAC)
Hetero atom,
And/or
R7And R8It is optionally C4To C20A part for carbocyclic ring system and indenyl carbon connected to it, preferably C5Ring, it is optional
Ground, a carbon atom can be replaced by nitrogen, sulphur or oxygen atom,
R9It is same or different to each other, and selected from group constituted by the following substances：The C of hydrogen, straight chain saturation1To C20Alkane
The undersaturated C of base, straight chain1To C20The C of alkyl, branch saturation1To C20The undersaturated C of alkyl, branch1To C20Alkyl, C3To C20
Cycloalkyl, C6To C20Aromatic radical, C7To C20Alkylaryl, C7To C20Aralkyl, OR10And SR10,
Preferably, R9It is same or different to each other, and is H or CH3,
Wherein,
R10As described above,
L is the bivalent group of two kinds of indenyl ligands of bridging, preferably C2R11 4Unit or SiR11 2Or GeR11 2, wherein,
R11Selected from group constituted by the following substances：H；The C of straight chain saturation1-C20The undersaturated C of alkyl, straight chain1To C20Alkane
The C of base, branch saturation1To C20The undersaturated C of alkyl, branch1To C20Alkyl, C3To C20Cycloalkyl, C6To C20Aromatic radical, C7Extremely
C20Alkylaryl and C7To C20Aralkyl, optionally the 14th~16 race comprising more than one periodic table (IUPAC)
Hetero atom,
It is preferred that Si (CH3)2、SiCH3C6H11Or SiPh2,
Wherein, C6H11It is cyclohexyl.
Preferably, the transistion metal compound of formula (II) is C2Symmetrical or vacation-C2It is symmetrical.About symmetry
Definition, it comments on (Chemical Reviews) with reference to Resconi etc., chemistry, volume 2000,100, the 4th phase, page 1263, and
And the document is incorporated herein.
Preferably, residue R1It is same or different to each other, it is more preferably mutually the same, and it is selected from constituted by the following substances
Group：The C of straight chain saturation1To C10The undersaturated C of alkyl, straight chain1To C10The C of alkyl, branch saturation1To C10Alkyl, branch are not
The C of saturation1To C10Alkyl and C7To C12Aralkyl.It is highly preferred that residue R1It is same or different to each other, it is more preferably mutually the same,
And it is selected from group constituted by the following substances：The C of straight chain saturation1To C6The undersaturated C of alkyl, straight chain1To C6Alkyl, branch
The C of chain saturation1To C6The undersaturated C of alkyl, branch1To C6Alkyl and C7To C10Aralkyl.It is more preferred still that residue R1That
This is identical or different, more preferably mutually the same, and it is selected from group constituted by the following substances：The C of linear chain or branch chain1To C4
Alkyl, such as such as methyl or ethyl.
Preferably, residue R2-R6It is same or different to each other, and the C that it is straight chain saturation1-C4Alkyl or branch saturation
C1-C4Alkyl.It is highly preferred that residue R2-R6It is same or different to each other, it is more preferably mutually the same, and it is selected from by following
The group that substance is formed：Methyl, ethyl, isopropyl and tertiary butyl.
Preferably, R7And R8It is same or different to each other, and it is 5- methylene basic rings to be selected from hydrogen and methyl or they
A part, the 5- methylenes basic ring include two indenyl ring carbons connected to it.In another preferred embodiment, R7It is selected from
OCH3And OC2H5, R8It is tertiary butyl.
In a preferred embodiment, transistion metal compound is bis- (the 2- first of racemization-methyl (cyclohexyl) silane diyl
Base -4- (4- tert-butyl-phenyls) indenyl) zirconium dichloride.
In the second preferred embodiment, transistion metal compound be racemization-dimethylsilane diyl it is bis- (2- methyl-
4- phenyl -1,5,6,7- tetrahydrochysenes-s-indacene -1- bases) zirconium dichloride.
In third preferred embodiment, transistion metal compound be racemization-dimethylsilane diyl it is bis- (2- methyl-
4- phenyl -5- methoxyl group -6- tertiary butyls indenyl) zirconium dichloride.
As further requirement, unit point solid particle catalyst according to the present invention must include co-catalyst, should
Co-catalyst includes the compound of the 13rd race's metal, such as Al compounds or boride.
Particularly preferably, B (C6F5)3、C6H5N(CH3)2H：B(C6F5)4、(C6H5)3C：B(C6F5)4Or Ni (CN)4[B
(C6F5)3]4 2-Borate co-catalyst.Suitable co-catalyst is as described in WO 2013/007650.
The example of Al co-catalysts is organo-aluminum compound, such as aluminium alkoxide compound.
This compound of Al, preferably aikyiaiurnirsoxan beta are used as unique compound in co-catalyst or can be with
It is used together with other cocatalyst compounds.Therefore, the change in addition to the compound of Al (i.e. aikyiaiurnirsoxan beta) or in addition to Al
Object (i.e. aikyiaiurnirsoxan beta) is closed, the other cationic complexes for forming cocatalyst compound, such as boron compound can also be used.
The co-catalyst is commercially available or can be prepared according to existing technical literature.It is preferable, however, that in solid catalysis
In the manufacture of agent system, only with the compound of Al as co-catalyst.
It is particularly preferred that co-catalyst is aikyiaiurnirsoxan beta, particularly C1To C10Alkylaluminoxane, most particularly methyl alumina
Alkane (MAO).
Preferably, the organic zirconate or organic hafnium compound of formula (I) or (II) and unit point solid particle are urged
The co-catalyst of agent show at least 70wt%, more preferably at least 80wt%, more preferably at least 90wt%, it is even further preferred that
The unit point solid particle catalyst of at least 95wt%.It is therefore preferred that unit point solid particle catalyst is characterized in that：
It is self-supported, i.e., it is not comprising any catalytically inactive carrier material, such as such as silica, aluminium oxide or MgCl2Or
Person's porous polymeric materials, the material are commonly used in heterogeneous catalysis system, i.e. catalyst is unsupported in outer carrier or carrier
On material.Since unit point solid particle catalyst is self-supported, thus it has rather low surface area.
In one embodiment, unit point solid particle catalyst is obtained by emulsifying curing technology, basic principle
As described in WO 03/051934.Herein, the document is all included by reference.
It is therefore preferred that unit point solid particle catalyst is in the form of solid catalyst particle, can by include with
The method of lower step obtains：
A) solution of more than one catalytic component is prepared；
B) solution is dispersed in the second solvent, to form lotion (wherein, more than one the catalytic component
It is present in the drop of dispersed phase),
C) dispersed phase is solidified, the drop is converted into solid particle, and optionally recycle the particle,
To obtain the catalyst.
It is preferable to use the first solvent, the solution is more preferably formed using the first organic solvent.It is it is more preferred still that organic
Solvent is selected from group constituted by the following substances：The alkane of straight chain, cricoid alkane, aromatic hydrocarbon and halogen-containing hydrocarbon.
In addition, the second solvent for forming continuous phase is inert solvent to catalytic component, at least in the dispersion steps phase
Between condition (such as temperature) under, the second solvent can be immiscible to the solution of catalytic component.Term is " molten with catalyst
Liquid is immiscible " refer to, the second solvent (continuous phase) and dispersed phase solution immiscible or part completely are immiscible (i.e. not completely
It dissolves each other with dispersed phase solution).
Preferably, immiscible solvent includes fluorinated organic solvent and/or the derivative of its functionalization, it is more preferred still that
Immiscible solvent includes half-, high-or fluoridized hydrocarbon and/or derivative of its functionalization.It is it is particularly preferred that described not mutual
Solvent includes perfluoro-hydrocarbon or the derivative of its functionalization, preferably C3-C30Perfluoro alkane ,-alkene or-cycloalkane, it is more excellent
Select C4-C10Perfluor-alkane ,-alkene either-the particularly preferred perflexane of cycloalkane, PF 5070, perfluorooctane or perfluor
(methyl cyclohexanol) or perfluor (1,3- dimethyl cyclohexane) or its mixture.
Further, it is preferable to ground, the lotion comprising the continuous phase and the dispersed phase be two-phase known in the art or
Heterogeneous system.Emulsification can be used to form and stable emulsion.After emulsion system is formed, the catalyst is by catalyst group
Divide and be formed in situ in the solution.
In principle, emulsifier can be the reagent of any suitable, be conducive to formation and/or the stabilization of lotion, and not
There is any detrimental effect to the catalytic activity of catalyst.Emulsifier for example can be based on the hydrocarbon for optionally using heteroatom interruptions
Surfactant, preferably optionally there is the halogenated hydrocarbons of functional group, semi-fluorinated hydrocarbon preferably known in the art, high fluorination
Hydrocarbon or fluoridized hydrocarbon.Optionally, emulsifier can be prepared, such as by will be before surfactant during prepared by lotion
Body is reacted with the compound of catalyst solution to be prepared.The surfactant precursor can have at least one functional group
Halogenated hydrocarbons, such as highly fluorinated C1-n (suitable for C4-30- or C5-15) alcohols (such as highly fluorinated enanthol, octanol or
Person's nonyl alcohol), oxide (such as propylene oxide (propenoxide)) or acrylate (such as rise anti-with cocatalyst component
Should, for example reacted with aikyiaiurnirsoxan beta and form " practical " surfactant).
In principle, it is possible to solid particle is formed from the drop of dispersion using arbitrary curing.According to one preferably
Embodiment, curing by temperature change processing realization.Therefore, lotion by most 10 DEG C/min, preferably 0.5~6 DEG C/
The gradual temperature change of min, more preferable 1~5 DEG C/min.It is further preferred that within less than 10 seconds, preferably smaller than 6 seconds, breast
Liquid passes through the temperature change more than 40 DEG C, preferably greater than 50 DEG C.
More specifically, continuous phase system and disperse phase system, lotion forming method, emulsifier and curing embodiment party
Formula and example, with reference to above-mentioned International Patent application WO 03/051934.
All or part of preparation process can be completed in a continuous manner.With reference to WO2006/069733, which depict pass through
The principle of this continuous or semi-continuous preparation method of solid catalyst type made from emulsification/curing.
Above-mentioned catalytic component is prepared according to the method described in WO 01/48034.
In the following, the present invention is further explained by embodiment.
Embodiment
1. measuring method
Unless otherwise indicated, the definition of following term and assay method be suitable for the invention above-mentioned general description and with
Lower embodiment.
Respectively, the second propylene-C is calculated4~C12The co-monomer content of alpha olefin copolymer component (C-PP2)：
Wherein,
W (PP1) is the first propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP1),
W (PP2) is the second propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP2),
C (PP1) is the first propylene-C4~C12The co-monomer content [wt%] of alpha olefin copolymer component (C-PP1),
C (PP) is propylene-C4~C12The co-monomer content [wt%] of alpha olefin copolymer component (C-PP),
C (PP2) is the co-monomer content [wt%] for the second propylene copolymer component (R-PP2) being computed.
Calculate the second propylene-C4~C12The cold soluble matter of dimethylbenzene (XCS) content of alpha olefin copolymer component (C-PP2)：
Wherein,
W (PP1) is the first propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP1),
W (PP2) is the second propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP2),
XS (PP1) is the first propylene-C4~C12The cold soluble matter of dimethylbenzene (XCS) of alpha olefin copolymer component (C-PP1)
Content [wt%],
XS (PP) is propylene-C4~C12The cold soluble matter of dimethylbenzene (XCS) content [wt%] of alpha olefin copolymer (C-PP),
XS (PP2) is the second propylene-C being computed4~C12The dimethylbenzene of alpha olefin copolymer component (C-PP2) is cold solvable
Object (XCS) content [wt%].
Calculate the second propylene-C4~C12The melt flow rate (MFR) MFR of alpha olefin copolymer component (C-PP2)2(230℃)：
Wherein,
W (PP1) is the first propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP1),
W (PP2) is the second propylene-C4~C12The weight fraction [wt%] of alpha olefin copolymer component (C-PP2),
MFR (PP1) is the first propylene-C4~C12The melt flow rate (MFR) MFR of alpha olefin copolymer component (C-PP1)2
(230 DEG C) [g/10min],
MFR (PP) is propylene-C4~C12The melt flow rate (MFR) MFR of alpha olefin copolymer (C-PP)2(230℃)[g/
10min],
MFR (PP2) is the second propylene-C being computed4~C12The melt flows speed of alpha olefin copolymer component (C-PP2)
Rate MFR2(230℃)[g/10min]。
Calculate the co-monomer content of elastomeric propylene copolymers (EC)：
Wherein,
Ww (PP) is propylene-C4~C12Alpha olefin copolymer component (C-PP) is i.e. at the first and second reactors (R1+R2)
The weight fraction [wt%] of the middle polymer prepared,
W (E) is that elastomeric propylene copolymers (EC) are prepared in third and optional 4th reactor (R3+R4)
The weight fraction [wt%] of polymer,
C (PP) is propylene-C4~C12The co-monomer content [wt%] of alpha olefin copolymer (C-PP), i.e., first and second
The co-monomer content [wt%] of the polymer prepared in reactor (R1+R2),
C (RAHECO) is the co-monomer content [wt%] of heterophasic propylene copolymers (RAHECO),
C (E) is the co-monomer content [wt%] for the elastomeric propylene copolymers (EC) being computed, i.e., in third and optionally
The co-monomer content [wt%] of the polymer prepared in 4th reactor (R3+R4).
MFR2(230 DEG C) are measured according to ISO 1133 (230 DEG C, load 2.16kg).
Number-average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD)
It is measured according to following methods by gel permeation chromatography (GPC)：
Weight average molecular weight Mw and molecular weight distribution (MWD=Mw/Mn, wherein, Mn is number-average molecular weight, and Mw is Weight-average molecular
Amount) by being based on ISO 16014-1：2003 and ISO 16014-4：2003 method measures.At 145 DEG C, in 1mL/
Under the constant flow rate of min, the Waters Alliance GPCV 2000 equipped with refractive index detector and in-line viscometer are used
Instrument has 3 TSK- gel columns (GMHXL-HT) and 1 from TosoHaas companies, and (TCB is used 2,4- trichloro-benzenes
2, the 6- di-t-butyl -4- methyl-phenols of 200mg/L are stablized) as solvent.The sample solution of 216.5 μ L of analysis injection every time.
Using with 19 narrow MWD polystyrene (PS) standards and one group of quilt in the range of 0.5kg/mol to 11500kg/mol
The relative scale of wide polypropylene standard preferably characterized calibrates column setting.All samples carry out by the following method
It prepares：The polymer of 5-10mg is dissolved in the TCB (being equivalent to mobile phase) of the stabilization of 10mL (at 160 DEG C), and
Continuous shaking is kept for 3 hours before sampling enters GPC instruments.
Pass through the co-monomer content of H NMR spectroscopy
Quantitative nuclear magnetic resonance (NMR) spectrum is used for steric regularity, region-regularity and the comonomer of quantifying polymers
Content.
For1H and13C uses the Bruker Advance run under 500.13MHz and 125.76MHz respectively
III500NMR spectrometers record quantitative in the molten state13C{1H } NMR spectra.Nitrogen is used for all atmosphere,
At 180 DEG C, use137mm Magic angle spinnings (MAS) probe best C, records all spectrum.The material of about 200mg is packed into 7mm
In outer diameter zirconium oxide MAS rotors, and rotated under 4kHz.The setting is selected primarily to rapid identification and accurate quantitatively institute
The high sensitivity needed.Using NOE the and RS-HEPT decoupled systems under short recycling delay, excited using the pulse of standard.It is right
Each spectrum obtains total 1024 (1k) a transient states.
To quantitative13C{1H } NMR spectra is handled, is integrated, and relevant quantization performance is determined by integrating.It is all
Chemical shift internally with reference to methyl isotaxy five-tuple (mmmm) at 21.85ppm.
Observe the characteristic signal corresponding to position defect and comonomer.
Pair arbitrary site unrelated with the stereosequence of intention is calibrated, and passes through the product in the methyl area between 23.6-19.7ppm
Point, quantitative steric regularity distribution.
Specifically, the quantitative influence of position defect and the distribution of comonomer tacticity carries out as follows
Correction：The integration of representative locations defect and comonomer is subtracted from the specific integrated area of stereosequence.
Isotacticity is measured at triad level, and is defined as complete with three unit group (mm) sequence phases
For the percentage of all trivalent basic sequences：
[mm] %=100 × (mm/ (mm+mr+rr))
Wherein, mr represents the summation of Reversible m r and rm trivalent basic sequence.
The presence of 2,1 erythro position defects is shown by the presence in two methyl sites at 17.7ppm and 17.2ppm
Show, and confirmed by other Q-character points.
The characteristic signal corresponding to other types of position defect is not observed.
The amount of 2,1 erythro position defects uses the average product in two feature methyl sites at 17.7ppm and 17.2ppm
Divide and quantified：
P21e=(Ie6+Ie8)/2
1, the 2 main amount for being inserted into propylene is quantized based on methyl area, wherein, to unrelated with being mainly inserted into the methyl area
It site and is corrected for the main insertion point being not included in the methyl area：
P12=ICH3+P12e
The total amount of propylene is quantified as main (1,2) and is inserted into propylene and all summation of other existing position defects：
PAlways=P12+P21e
The molar percentage of 2,1 erythro position defects is quantified relative to whole propylene：
[21e] mol%=100 × (P21e/PAlways)
It observes corresponding to C5-12The characteristic signal that alpha-olefin is incorporated to.It (is calculated using the integration of corresponding site relative to every
The number in the report site of comonomer), to being incorporated to PPC5-12The C of isolated amount in PP sequences5-12Alpha-olefin is quantified.
It is right using the integration (number for calculating the report site relative to every comonomer) in the α B4 sites at 44.1ppm
Alkene is quantified the 1- for the isolated amount being incorporated in PPHPP sequences：
H=I [α B4]/2
In the case where not observing the site that display is continuously incorporated to, only calculating total 1- with this amount, alkene comonomer contains
Amount：
HAlways=H
It is right using the integration (number for calculating the report site relative to every comonomer) in the α B6 sites at 44.0ppm
The 1- octenes for the isolated amount being incorporated in PPOPP sequences are quantified：
O=I [α B6]/2
In the case where not observing the site that display is continuously incorporated to, total 1- octene co-monomers are only calculated with this amount and are contained
Amount：
OAlways=O
Observation corresponds to the characteristic signal that ethylene is incorporated to.
Using the S α γ sites at 37.8ppm integration (calculate relative to every comonomer report site number),
The ethylene of isolated amount to being incorporated in PPEPP sequences quantifies：
E=I [S α γ]/2
It is right using the integration (number for calculating the report site relative to every comonomer) in the S β δ sites at 26.9ppm
The ethylene of the continuous amount of being incorporated in PPEEPP sequences is quantified：
EE=IS β δ
The site that another type of ethylene is incorporated to, such as PPEPEPP and PPEEEPP are shown, by the spy as EPE and EEE
Reference number quantifies, and by with PPEEPP sequences it is same in a manner of calculated.Based on isolated, continuous and discrete
The summation for the ethylene being incorporated to calculates total ethylene comonomer content：
EAlways=E+EE+EPE+EEE
The total moles score of comonomer in polymer is calculated as：
fE=(EAlways/(EAlways+PAlways+C5-12；Always)
fC5-12=(EAlways/(EAlways+PAlways+C5-12；Always)
The molar percentage of the comonomer amount of being incorporated in polymer is calculated according to the following formula, from molar fraction：
[C5-12] mol%=100 × fC5-12
[E] mol%=100 × fE
The weight percent of alkene and ethylene calculates the 1- being incorporated in polymer according to the following formula, from molar fraction：
[H] wt%=100 × (fH×84.16)/((fE×28.05)+(fH×84.16)+((1-(fE+fH))×
42.08))
[E] wt%=100 × (fE×28.05)/((fE×28.05)+(fH×84.16)+((1-(fE+fH))×
42.08))
The 1- octenes and the weight percent of ethylene being incorporated in polymer are calculated according to the following formula, from molar fraction：
[O] wt%=100 × (fO×112.21)/((fE×28.05)+(fO×112.21)+((1-(fE+fO))×
42.08))
[E] wt%=100 × (fE×28.05)/((fE×28.05)+(fO×112.21)+((1-(fE+fO))×
42.08))
Inherent viscosity：It is measured according to DIN ISO in October, 1628/1,1999 (in naphthalane, at 135 DEG C).
Xylene soluble part (XCS, wt%)：According to the 16152 (first editions of ISO；2005-07-01), it at 25 DEG C, measures
The content of the cold soluble matter of dimethylbenzene (XCS).The insoluble part of remaining is the cold insoluble matter of dimethylbenzene (XCI) fraction.
Hexane Extractable component：In the monolayer cast film line of the melting temperature with 220 DEG C and 20 DEG C of chill-roll temperature
In the casting films of 100 μ m thicks of upper preparation, according to FDA methods (federal registration, the 21st, the 1st chapter, the 177th part, the 1520th
Section, referring to Appendix B) it is measured.At 50 DEG C of temperature and the extraction time of 30min, extracted.
Melting temperature (Tm) and heat of fusion (Hf), crystallization temperature (Tc) and crystallization heat (Hc)：On the sample of 5~10mg, make
It is measured with Mettler TA820 differential scanning calorimeters (DSC).According to ISO 11357-3：1999 ,+23 DEG C~+210
Within the temperature range of DEG C, in the heating of the sweep speed of 10 DEG C/min/cooling/heating cycle, DSC is run.Crystallization temperature
With crystallization heat (Hc) measured by cooling step, and melting temperature and heat of fusion (Hf) then measured by the second heating stepses.All material
With more than one fusing point, but one main one be showed more than 50% total melting enthalpy.
Glass transition temperature Tg is measured according to ISO6721-7 by dynamic mechanical analysis.With the heating speed of 2 DEG C/min
With the frequency of 1Hz, between -100 DEG C and+150 DEG C, in compression moulded samples (40 × 10 × 1mm3) in, it completes to survey in the torsional mode
Amount.
50 μ m thicks prepared on the monolayer cast film line of the melting temperature with 220 DEG C and 20 DEG C of chill-roll temperature
Casting films on, at 23 DEG C, stretch modulus in machine direction and horizontal direction is measured according to ISO 527-1.With 1mm/
The crosshead speed of min implements experiment.
Charpy notch impact strength according to 179 1eA of ISO, under conditions of 23 ° and -20 DEG C, by using according to EN
80 × 10 × 4mm of ISO 1873-2 injection moldings3Test bar be measured.
Stress whitening (stress-whitening) is specific as described in 1 860 147A1 of EP, size be 125 ×
It is measured in the injection molding UL94 test pieces of 12.5 × 2mm (length × width x thickness).
On the universal testing machine (Zwick Z010) of the test speed with 50mm/min, in reversed three point bending test
The middle measure for implementing stress whitening.Technical term (for example, deflection, supporter, load edge) in this specific experimental method
Definition as described in ISO178 (bend test).
Measure two different parameters：
I. stress whitening angle [°] is the bending angle at stress whitening appearance.The appearance of stress whitening is equivalent to specific
Tilt value be bent during optic response drastically decline.
Ii. remaining stress whitening 90 ° [mm] is the residual ruler in (blushing) region rubescent immediately after 90 ° of bendings
It is very little.Bend test is proceeded to 90 ° of bending angle.Then, sample is discharged with the crosshead speed of 400mm/min.After release
The length (length direction for being parallel to sample measures) in rubescent (blushing) region measured immediately is remaining stress whitening
90°。
Average grain diameter (d50) is to be measured at room temperature, using Coulter Counter LS200, wherein, normal heptane
As medium, 100nm is less than by the particle size of transmission electron microscopy.
2. embodiment
It is used in the polymerization for the heterophasic propylene copolymers of IE1 and IE2 of the embodiment of the present invention (RAHECO)
Catalyst is the metallocene catalyst as described in the embodiment 10 of WO 2010/052263A1.
CE1 is the business atactic propene copolymer " Borpact SH950MO " of Borealis.
CE2 is the business atactic propene copolymer " BorPure RG466MO " of Borealis.
CE3 is the business random-heterophasic co-polymer " BorSoft SD233CF " of Borealis.
Table 1：Polymerizing condition
| IE 1 | IE 2 | ||
| Loop | |||
| Temperature | [℃] | 65 | 6 5 |
| Ratio | [%] | 34 | 36 |
| H2/C3 ratios | [mol/kmol] | 0.21 | 0.21 |
| C3/C6 ratios | [mol/kmol] | 8.8 | 8.8 |
| MFR2 | [g/10min] | 33 | 33 |
| XCS | [wt%] | 1.2 | 1.3 |
| C6 contents | [wt%] | 1.2 | 1.2 |
| GPR 1 | |||
| Temperature | [℃] | 85 | 8 5 |
| Pressure | [kPa] | 2300 | 2300 |
| Ratio | [%] | 42 | 44 |
| H2/C3 ratios | [mol/kmol] | 1.0 | 1.3 |
| C3/C6 ratios | [mol/kmol] | 0.4 | 0.4 |
| MFR2 | [g/10min] | 34 | 44 |
| XCS | [wt%] | 1.5 | 1.2 |
| C6 contents | [wt%] | 3.4 | 3.4 |
| GPR 2 | |||
| Temperature | [℃] | 80 | 8 0 |
| Pressure | [kPa] | 2500 | 2500 |
| Ratio | [%] | 24 | 22 |
| C2/C3 ratios | [mol/kmol] | 10727 | 10504 |
| H2 is fed | [mol] | No | No |
| MFR2 | [g/10min] | 19 | 25 |
| XCS | [wt%] | 17.5 | 14.2 |
| C2 contents | [wt%] | 19.4 | 19.2 |
| C6 contents | [wt%] | 2.4 | 2.1 |
C2 ethylene
C6 1- alkene
The ratio of H2/C3 ratios hydrogen/propylene
The ratio of C6/C3 ratios 1- alkene/propylene
The gas-phase reactor of the first gas-phase reactor of 1/2GPR/second
Loop loop reactor
Table 2：Performance
| IE 1 | IE 1a | IE 2 | IE 2a | CE 1 | CE 2 | CE 3 | ||
| MFR2 | [g/10min] | 19 | 19 | 25 | 25 | 26 | 30 | 7 |
| Tm(PE) | [℃] | 135 | 135 | 128 | 128 | 102 | - | 111 |
| Hm(PE) | [J/g] | 3.2 | 3.0 | 4.0 | 3.8 | 1.1 | - | 0.4 |
| Tm(PP,1) | [℃] | 135 | 135 | 128 | 128 | 158 | 137 | 141 |
| Hm(PP,1) | [J/g] | 3.2 | 3.5 | 3.5 | 3.7 | 1.1 | 62.8 | 59.8 |
| Tm(PP,2) | [℃] | 141 | 141 | 143 | 143 | 163 | 151 | 151 |
| Hm(PP,2) | [J/g] | 70.0 | 77.8 | 71.5 | 78.8 | 69.9 | 28.3 | 1.9 |
| Tc | [℃] | 96 | 116 | 97 | 112 | 109 | 112 | 100 |
| The Tg (1) of M | [℃] | 5.9 | 5.9 | 5.8 | 5.8 | 0.0 | -3.8 | -3.7 |
| The Tg (2) of E | [℃] | -31.8 | -31.8 | -31.8 | -31.8 | -54.0 | - | -50.0 |
| Total C2 | [wt%] | 19.4 | 19.4 | 19.2 | 19.2 | 24.4 | 4.1 | 8.0 |
| Total C6 | [wt%] | 2.4 | 2.4 | 2.1 | 2.1 | - | - | - |
| XCS | [wt%] | 16.6 | 16.6 | 13.6 | 13.6 | 16.4 | 9.0 | 20.0 |
| The IV of XCS | [dl/g] | 1.8 | 1.8 | 1.8 | 1.8 | 1.7 | n.d. | 1.3 |
| The C2 of XCS | [wt%] | 78.0 | 78.0 | 78.0 | 78.0 | 47.0 | n.d. | 39.0 |
| The C2 of XCI | [wt%] | 4.6 | 4.6 | 4.6 | 4.6 | n.d. | n.d. | n.d. |
| The C6 of XCI | [wt%] | 2.9 | 2.9 | 2.9 | 2.9 | - | - | - |
| C6(FDA)100μm CF | [wt%] | 2.7 | n.d. | 1.7 | n.d | 3.7 | 2.8 | 4.0 |
| Stretch modulus | [MPa] | 570 | 770 | 630 | 744 | 950 | 1050 | 500 |
| 23 DEG C of Charpy notch impact strength | [kJ/m2] | 9.8 | 7.6 | 6.6 | 8.1 | 7.9 | 3.9 | 10.0 |
| - 20 DEG C of Charpy notch impact strength | [kJ/m2] | 3.4 | 2.1 | 2.1 | 2.1 | 2.0 | 1.0 | 1.0 |
| Mist degree | [%] | 41.7 | 20.5 | 46.8 | 22.1 | 55.6 | 17.7 | 68.0 |
IE 1a use the 1,3 of 0.2wt%：2,4 two (methylbenzilidene) sorbierite (cities of DMDBS, Milliken company
Sell Millad 3988, the U.S.) nucleation
IE 2a use hydroxyl-bis- [2,2 '-methylene-bis- (4, the 6- di-tert-butyl-phenyl) phosphoric acid] aluminium and meat of 0.2wt%
The mixture nucleation of myristic acid lithium (the commercially available Adekastab NA-21 of Adeka Palmarole companies, France)
N.d.-do not detect
At 220 DEG C, in corotating double screw extruder Coperion ZSK 57, by all polymer powders with
The Irganox B225 (1 of 0.2wt%：(four (3- (3 ', the 5 '-di-t-butyl -4- hydroxy-methylbenzenes of Irganox 1010 of 1- blendings
Base)-propionic acid) pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphoric acid) phosphite ester) (BASF AG, Germany), 0.1wt%
Calcium stearate and 0.2wt% nucleating agent Millad 3988 or Adekastab NA-21 (if present) it is mixed
It closes.
Table 3：Stress whitening
Claims (19)
1. heterophasic propylene copolymers RAHECO, it includes：
(i) matrix M is propylene-C4~C12Alpha olefin copolymer C-PP, the propylene-C4~C12Alpha olefin copolymer C-PP
Include the unit from following substance：
(i.1) propylene and
(i.2) at least one C4~C12Alpha-olefin；And
(ii) the elastomeric propylene copolymers EC being scattered in the matrix M, the elastomeric propylene copolymers EC include be derived from
The unit of lower substance：
(ii.1) propylene and
(ii.2) ethylene and optional at least one C4~C12Alpha-olefin；
The heterophasic propylene copolymers RAHECO has：
(a) according to the melt flow rate (MFR) MFR at 230 DEG C of the measurements of ISO 11332In the range of 2.5~200.0g/10min；
(b) total comonomer content is in the range of 12.0~35.0wt%；
(c) amount of the cold soluble matter XCS fractions of dimethylbenzene measured at 25 DEG C according to ISO 16152 is 10.0~40.0wt%；
(d) total comonomer content of the cold soluble matter XCS fractions of dimethylbenzene is in the range of 60.0~90.0wt%；
Wherein, further, the heterophasic propylene copolymers RAHECO meets：
(e) inequality (I)
Wherein,
C2 (total) is the ethylene contents of heterophasic propylene copolymers RAHECO, in terms of wt%；
Cx (total) is the C of heterophasic propylene copolymers RAHECO4~C12Alpha-olefin content, in terms of wt%.
2. heterophasic propylene copolymers RAHECO according to claim 1, wherein,
(a) ethylene contents in total heterophasic propylene copolymers RAHECO in terms of wt% are in the range of 12.0~33.0wt%；
Or
(b) C in total heterophasic propylene copolymers RAHECO in terms of wt%4~C12Alpha-olefin content is in 0.5~6.0wt% ranges
It is interior.
3. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein,
(a) propylene-C4~C12Alpha olefin copolymer C-PP is propylene -1- alkene copolymer C6-PP；
Or
(b) elastomeric propylene copolymers EC is ethylene-propylene rubber EPR.
4. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein, heterophasic propylene copolymers RAHECO's
The cold soluble matter XCS fractions of dimethylbenzene are according to DIN ISO 1628/1, the inherent viscosity IV measured in naphthalane, at 135 DEG C
At least 1.2dl/g.
5. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein, heterophasic propylene copolymers RAHECO's
The cold insoluble matter XCI fractions of dimethylbenzene：
(a) weight based on the cold insoluble matter XCI fractions of dimethylbenzene has total in the range of 3.0~12.0wt% in terms of wt%
Co-monomer content,
Or
(b) total weight based on the cold insoluble matter XCI fractions of dimethylbenzene has in terms of wt% in the range of 2.0~11.0wt%
Ethylene contents；
Or
(c) total weight based on the cold insoluble matter XCI fractions of dimethylbenzene has the C in terms of wt% in the range of 0.5~6.0wt%4
~C12Alpha-olefin content；
Or
(d) meet inequality (II)
Wherein,
C2 (XCI) be heterophasic propylene copolymers RAHECO the cold insoluble matter XCI fractions of dimethylbenzene in ethylene contents in terms of wt%；
Cx (XCI) be heterophasic propylene copolymers RAHECO the cold insoluble matter XCI fractions of dimethylbenzene in C in terms of wt%4~C12α-
Olefin(e) centent.
6. heterophasic propylene copolymers RAHECO according to claim 1 or 2 meets：
(a) inequality (III)
Wherein,
C (XCS) be heterophasic propylene copolymers RAHECO the cold soluble matter XCS fractions of dimethylbenzene in total comonomer in terms of wt%
Content；
C (total) is the total comonomer content in terms of wt% in total heterophasic propylene copolymers RAHECO；
Or
(b) inequality (IV)
Wherein,
C2 (XCS) be heterophasic propylene copolymers RAHECO the cold soluble matter XCS fractions of dimethylbenzene in ethylene contents in terms of wt%；
C2 (total) is the ethylene contents in terms of wt% in total heterophasic propylene copolymers RAHECO；
Or
(c) inequality (V)
Wherein,
C2 (XCS) be heterophasic propylene copolymers RAHECO the cold soluble matter XCS fractions of dimethylbenzene in ethylene contents in terms of wt%；
C (XCI) be heterophasic propylene copolymers RAHECO the cold insoluble matter XCI fractions of dimethylbenzene in total comonomer in terms of wt%
Content；
Or
(d) inequality (VI)
Wherein,
C2 (XCS) be heterophasic propylene copolymers RAHECO the cold soluble matter XCS fractions of dimethylbenzene in ethylene contents in terms of wt%；
C2 (XCI) be heterophasic propylene copolymers RAHECO the cold insoluble matter XCI fractions of dimethylbenzene in ethylene contents in terms of wt%.
7. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein, propylene-C4~C12Alpha olefin copolymer
C-PP includes the first polypropylene component PP1 and the second propylene-C4~C12Alpha olefin copolymer component C-PP2.
8. heterophasic propylene copolymers RAHECO according to claim 7, wherein,
(a) propylene-C4~C12Co-monomer content in alpha olefin copolymer C-PP in terms of wt% is higher than the first polypropylene component
Co-monomer content in PP1 in terms of wt%；
Or
(b) the first polypropylene component PP1 and propylene-C4~C12Co-monomer content between alpha olefin copolymer C-PP differ to
Few 1.5wt%；
Or
(c) the first polypropylene component PP1 and the second propylene-C4~C12Comonomer between alpha olefin copolymer component C-PP2
Content differs at least 2.5wt%.
9. heterophasic propylene copolymers RAHECO according to claim 8, wherein, the first polypropylene component PP1 is：
(a) propylene homopolymer component H-PP1；
Or
(b) the first propylene-C4~C12Alpha olefin copolymer component C-PP1.
10. heterophasic propylene copolymers RAHECO according to claim 8, wherein,
(a) the second propylene-C4~C12C in alpha olefin copolymer component C-PP24~C12Alpha-olefin content 2.0~
In the range of 15.0wt%；
Or
(b) propylene-C4~C12Co-monomer content in alpha olefin copolymer C-PP is in the range of 1.5~9.0wt%；
11. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein, the copolymerization of elastomeric propylene copolymers EC
Content of monomer is in the range of 40~90wt%.
12. heterophasic propylene copolymers RAHECO according to claim 1 or 2 meets inequality (VIII)：
Wherein,
C (total) is the total comonomer content in heterophasic propylene copolymers RAHECO in terms of wt%；
XCS is the content of the cold soluble matter XCS fractions of dimethylbenzene of heterophasic propylene copolymers RAHECO, in terms of wt%.
13. heterophasic propylene copolymers RAHECO according to claim 1 or 2 has the first glass transition temperature Tg
(1) and the second glass transition temperature Tg (2), wherein, first glass transition temperature Tg (1) turns higher than the second vitrifying
Temperature Tg (2).
14. heterophasic propylene copolymers RAHECO according to claim 13, has：
(a) the first glass transition temperature Tg (1) in the range of -5~+12 DEG C；
Or
(b) the second glass transition temperature Tg (2) in the range of -45~-25 DEG C.
15. heterophasic propylene copolymers RAHECO according to claim 1 or 2, wherein, the heterophasic propylene copolymers
RAHECO is through α-nucleation.
16. heterophasic propylene copolymers RAHECO according to claim 1 or 2, has：
(a) it is at least 500MPa according to the ISO 527-1 stretch moduluses measured at 23 DEG C,
Or
(b) 3.0wt% is less than according to the hexane extractable content that FDA methods measure in 100 μm of casting films.
17. being used to prepare the method for heterophasic propylene copolymers RAHECO according to any one of the preceding claims, wrap
Include following steps：
(I) polypropylene and C4~C12Alpha-olefin, so as to form matrix M i.e. propylene-C4~C12Alpha olefin copolymer C-PP；And
(II) then, polypropylene and ethylene, optional at least one C4~C12Alpha-olefin is scattered in the matrix so as to be formed
Elastomeric propylene copolymers EC in M；
Wherein, step (I) and step (II) both carry out in the presence of identical unit point solid particle catalyst, unit
Point solid particle catalyst includes following substance：
(i) complex compound of formula (I)：
Rn(Cp’)2MX2 (I)
Wherein,
" M " is zirconium Zr or hafnium Hf,
Each " X " independently is univalent anion σ-ligand,
Each " Cp ' " is cyclopentadienyl type organic ligand, independently selected from constituted by the following substances
Group：Substituted cyclopentadienyl group, the indenyl of substitution, the tetrahydro indenyl of substitution and substituted or unsubstituted fluorenyl, it is described
Organoligand coordination in transition metal M,
" R " is the divalent bridging group for connecting the organic ligand Cp ',
" n " be 1 or 2 and
(ii) co-catalyst, it includes the compounds of the 13rd race's metal.
18. according to the method for claim 17, wherein, step (I) includes：Polypropylene and optional C4~C12α-alkene
Hydrocarbon, so as to form the first polypropylene component PP1, then polypropylene and C in another reactor4~C12Alpha-olefin, so as to shape
Into the second propylene-C4~C12Alpha olefin copolymer component C-PP2, the first polypropylene component PP1 and the second propylene-C4~C12α-alkene
Hydrocarbon copolymer component C-PP2 forms propylene-C4~C12Alpha olefin copolymer C-PP.
19. a kind of product, it includes the heterophasic propylene copolymers according to any one of the claims 1~16
RAHECO。
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| EP3184587B1 (en) * | 2015-12-21 | 2020-03-18 | Borealis AG | Extruded articles with improved optical properties |
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